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1.
Int J Biometeorol ; 67(12): 1927-1940, 2023 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-37726553

RESUMEN

Hot weather conditions can have negative impacts on the thermal comfort and physical activity of vulnerable groups such as children. The aim of this study is to analyze the effects of warm weather on 5-year-old children's thermal comfort and physical activity in a preschool yard in Gothenburg, Sweden. In situ measurements were conducted for 1-1.5 h in the early afternoon on 8 days in May, June, and August of 2022. The thermal comfort and physical activity was estimated with GPS-tracks, heart rate monitors, and step counts and compared to observed weather conditions. Results show that physical activity decreases under warmer weather conditions, depicted by a decrease in distance moved, step counts, and highest registered pulse. Moreover, on warm days, the children avoid sunlit areas. For 50% or more of the time spent in sunlit areas, the children are exposed to cautious levels of heat. In shaded areas, on the other hand, the children are less exposed, with five out of 8 days having 50% or more of the time at neutral levels. The study demonstrates the importance of access to shaded areas in preschool yards where children can continue their active play while simultaneously maintaining a safe thermal status.


Asunto(s)
Ejercicio Físico , Tiempo (Meteorología) , Humanos , Preescolar , Suecia , Instituciones Académicas , Escolaridad
2.
Int J Biometeorol ; 67(4): 633-647, 2023 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-36826592

RESUMEN

A robust representation of the radiative properties in complex urban settings is important for accurate estimations of radiant load. Here, we present a new parameterization scheme in the SOlar and LongWave Environmental Irradiance Geometry (SOLWEIG) model that partitions the upper hemisphere into 153 patches. Partitioning of the upper hemisphere enables determination if longwave irradiance originates from the sky, vegetation, sunlit building surfaces, or shaded building surfaces from each patch. Furthermore, a model for anisotropic sky longwave irradiance where emissivity increases with zenith angle is included. Comparisons between observations and simulations show high correlation, with R2 and RMSE for Tmrt of 0.94 and 4.6 °C, respectively, and R2 and RMSE for longwave radiation of 0.89 and 14.1 Wm-2, respectively. Simulations show that mean radiant temperature (Tmrt) can be up to 1.5 °C higher with an anisotropic sky compared to a uniform sky as an effect of higher radiant load on the vertical of a human when sky longwave irradiance increases with zenith angle. In comparisons of simulated Tmrt with the new parameterization and old parameterization schemes, previously overestimated Tmrt under trees (high sky obstruction, sky view factor (SVF) < 0.3) can be decreased by up to 3 °C from more realistic estimations using the patches. Moreover, Tmrt close to sunlit walls (SVF ~ 0.5) is increased by up to 2-3 °C from increased exposure to sunlit surfaces. Concluding, anisotropic sky longwave radiation and directionality of longwave radiation from different sources are important in estimations of Tmrt of humans in outdoor settings.


Asunto(s)
Modelos Teóricos , Luz Solar , Humanos , Temperatura
3.
Br J Sports Med ; 55(15): 825-830, 2021 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-32467149

RESUMEN

BACKGROUND: The Wet-Bulb Globe Temperature (WBGT) index is a common tool to screen for heat stress for sporting events. However, the index has a number of limitations. Rational indices, such as the physiological equivalent temperature (PET) and Universal Thermal Climate Index (UTCI), are potential alternatives. AIM: To identify the thermal index that best predicts ambulance-required assistances and collapses during a city half marathon. METHODS: Eight years (2010-2017) of meteorological and ambulance transport data, including medical records, from Gothenburg's half-marathon were used to analyse associations between WBGT, PET and UTCI and the rates of ambulance-required assistances and collapses. All associations were evaluated by Monte-Carlo simulations and leave-one-out-cross-validation. RESULTS: The PET index showed the strongest correlation with both the rate of ambulance-required assistances (R2=0.72, p=0.008) and collapses (R2=0.71, p=0.008), followed by the UTCI (R2=0.64, p=0.017; R2=0.64, p=0.017) whereas the WBGT index showed substantially poorer correlations (R2=0.56, p=0.031; R2=0.56, p=0.033). PET stages of stress, match the rates of collapses better that the WBGT flag colour warning. Compared with the PET, the WBGT underestimates heat stress, especially at high radiant heat load. The rate of collapses increases with increasing heat stress; large increase from the day before the race seems to have an impact of the rate of collapses. CONCLUSION: We contend that the PET is a better predictor of collapses during a half marathon than the WBGT. We call for further investigation of PET as a screening tool alongside WBGT.


Asunto(s)
Aire , Ambulancias/estadística & datos numéricos , Temperatura Corporal/fisiología , Agotamiento por Calor/epidemiología , Carrera/estadística & datos numéricos , Termografía/métodos , Adolescente , Adulto , Distribución por Edad , Anciano , Regulación de la Temperatura Corporal , Intervalos de Confianza , Femenino , Agotamiento por Calor/diagnóstico , Trastornos de Estrés por Calor , Respuesta al Choque Térmico , Humanos , Humedad , Modelos Lineales , Masculino , Carrera de Maratón , Persona de Mediana Edad , Método de Montecarlo , Riesgo , Carrera/fisiología , Distribución por Sexo , Temperatura Cutánea/fisiología , Luz Solar , Suecia/epidemiología , Termografía/instrumentación , Sensación Térmica , Factores de Tiempo , Viento , Adulto Joven
4.
Scand J Med Sci Sports ; 28(12): 2760-2766, 2018 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-30218614

RESUMEN

OBJECTIVES: Despite endurance races leading to a substantial number of ambulance-requiring cases (ARC), little is known regarding where they occur, meaning that knowing where to place medical teams, ambulance pick-up points, etc, is difficult. This article investigates whether the location of ARCs can be identified by race participants. METHODS: Using the world's largest half marathon (Gothenburg half marathon) as a case, 237 runners were asked, post-race, to mark on a map which geographical point of the race was most exhausting. Using the level of agreement tests, these geographical points were then compared with the GPS positions of ARCs. RESULTS: According to the level of agreement tests, the most exhausting positions (MEP), as identified by participants, seem to be highly correlated to the location of ARCs. This study can also show that ambulance-requiring cases seem to be more prevalent towards the end of the race and in uphill sections. CONCLUSIONS: By asking participants where they found the race most exhausting it seems possible to identify high-risk places for an ARC. From a practical perspective, using this method could considerably increase the safety of competitors as well as improving the cost-effectiveness of safety interventions at endurance races. Further studies are needed to understand the specific risk factors of the high-risk areas as well as characteristics of collapsed runners.


Asunto(s)
Ambulancias , Fatiga/diagnóstico , Predicción , Carrera , Femenino , Geografía , Humanos , Masculino , Factores de Riesgo
5.
Int J Biometeorol ; 61(9): 1531-1543, 2017 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-28447175

RESUMEN

Present-day and projected future changes in mean radiant temperature, T mrt in one northern, one mid-, and one southern European city (represented by Gothenburg, Frankfurt, and Porto), are presented, and the concept of hot spots is adopted. Air temperature, T a , increased in all cities by 2100, but changes in solar radiation due to changes in cloudiness counterbalanced or exacerbated the effects on T mrt. The number of days with high T mrt in Gothenburg was relatively unchanged at the end of the century (+1 day), whereas it more than doubled in Frankfurt and tripled in Porto. The use of street trees to reduce daytime radiant heat load was analyzed using hot spots to identify where trees could be most beneficial. Hot spots, although varying in intensity and frequency, were generally confined to near sunlit southeast-southwest facing walls, in northeast corner of courtyards, and in open spaces in all three cities. By adding trees in these spaces, the radiant heat load can be reduced, especially in spaces with no or few trees. A set of design principles for reducing the radiant heat load is outlined based on these findings and existing literature.


Asunto(s)
Planificación de Ciudades , Temperatura , Ciudades , Cambio Climático , Predicción , Alemania , Modelos Teóricos , Portugal , Luz Solar , Suecia , Árboles
6.
Angew Chem Int Ed Engl ; 54(36): 10675-80, 2015 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-26206667

RESUMEN

The controversial nature of chemical bonding between noble gases and noble metals is addressed. Experimental evidence of exceptionally strong Au-Ar bonds in Ar complexes of mixed Au-Ag trimers is presented. IR spectra reveal an enormous influence of the attached Ar atoms on vibrational modes, particularly in Au-rich trimers, where Ar atoms are heavily involved owing to a relativistically enhanced covalency. In Ag-rich trimers, vibrational transitions of the metal framework predominate, indicating a pure electrostatic character of the Ag-Ar bonds. The experimental findings are analyzed by means of DFT calculations, which show how the relativistic differences between Au and Ag are manifested in stronger Au-Ar binding energies. Because of the ability to vary composition and charge distribution, the trimers serve as ideal model systems to study the chemical nature of the bonding of noble gases to closed-shell systems containing gold.

7.
Mutat Res ; 777: 23-32, 2015 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-25916945

RESUMEN

Chemotherapy and radiotherapy can cause permanent damage to the genomes of surviving cells, provoking severe side effects such as second malignancies in some cancer survivors. Drugs that mimic the activity of death ligands, or antagonise pro-survival proteins of the Bcl-2 or IAP families have yielded encouraging results in animal experiments and early phase clinical trials. Because these agents directly engage apoptosis pathways, rather than damaging DNA to indirectly provoke tumour cell death, we reasoned that they may offer another important advantage over conventional therapies: minimisation or elimination of side effects such as second cancers that result from mutation of surviving normal cells. Disappointingly, however, we previously found that concentrations of death receptor agonists like TRAIL that would be present in vivo in clinical settings provoked DNA damage in surviving cells. In this study, we used cell line model systems to investigate the mutagenic capacity of drugs from two other classes of direct apoptosis-inducing agents: the BH3-mimetic ABT-737 and the IAP antagonists LCL161 and AT-406. Encouragingly, our data suggest that IAP antagonists possess negligible genotoxic activity. Doses of ABT-737 that were required to damage DNA stimulated Bax/Bak-independent signalling and exceeded concentrations detected in the plasma of animals treated with this drug. These findings provide hope that cancer patients treated by BH3-mimetics or IAP antagonists may avoid mutation-related illnesses that afflict some cancer survivors treated with conventional DNA-damaging anti-cancer therapies.


Asunto(s)
Supervivencia Celular/efectos de los fármacos , Proteínas Inhibidoras de la Apoptosis/genética , Mutación , Proteína X Asociada a bcl-2/genética , Animales , Antineoplásicos/farmacología , Apoptosis/efectos de los fármacos , Azocinas/farmacología , Compuestos de Bencidrilo/farmacología , Compuestos de Bifenilo/farmacología , Línea Celular Tumoral , Ensayo Cometa , Daño del ADN/efectos de los fármacos , Relación Dosis-Respuesta a Droga , Proteínas Inhibidoras de la Apoptosis/antagonistas & inhibidores , Proteínas Inhibidoras de la Apoptosis/metabolismo , Ratones , Mutágenos/farmacología , Nitrofenoles/farmacología , Piperazinas/farmacología , Sulfonamidas/farmacología , Tiazoles/farmacología , Proteína X Asociada a bcl-2/antagonistas & inhibidores , Proteína X Asociada a bcl-2/metabolismo
8.
Int J Biometeorol ; 59(7): 799-814, 2015 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-25218492

RESUMEN

Future anthropogenic climate change is likely to increase the air temperature (T(a)) across Europe and increase the frequency, duration and magnitude of severe heat stress events. Heat stress events are generally associated with clear-sky conditions and high T(a), which give rise to high radiant heat load, i.e. mean radiant temperature (T(mrt)). In urban environments, T mrt is strongly influenced by urban geometry. The present study examines the effect of urban geometry on daytime heat stress in three European cities (Gothenburg in Sweden, Frankfurt in Germany and Porto in Portugal) under present and future climates, using T(mrt) as an indicator of heat stress. It is found that severe heat stress occurs in all three cities. Similar maximum daytime T(mrt) is found in open areas in all three cities despite of the latitudinal differences in average daytime T(mrt). In contrast, dense urban structures like narrow street canyons are able to mitigate heat stress in the summer, without causing substantial changes in T(mrt) in the winter. Although the T(mrt) averages are similar for the north-south and east-west street canyons in each city, the number of hours when T(mrt) exceeds the threshold values of 55.5 and 59.4 °C-used as indicators of moderate and severe heat stress-in the north-south canyons is much higher than that in the east-west canyons. Using statistically downscaled data from a regional climate model, it is found that the study sites were generally warmer in the future scenario, especially Porto, which would further exacerbate heat stress in urban areas. However, a decrease in solar radiation in Gothenburg and Frankfurt reduces T(mrt) in the spring, while the reduction in T(mrt) is somewhat offset by increasing T(a) in other seasons. It suggests that changes in the T(mrt) under the future scenario are dominated by variations in T(a). Nonetheless, the intra-urban differences remain relatively stable in the future. These findings suggest that dense urban structure can reduce daytime heat stress since it reduces the number of hours of high T(mrt) in the summer and does not cause substantial changes in average and minimum T(mrt) in the winter. In dense urban settings, a more diverse urban thermal environment is also preferred to compensate for reduced solar access in the winter. The extent to which the urban geometry can be optimized for the future climate is also influenced by local urban characteristics.


Asunto(s)
Planificación de Ciudades , Cambio Climático , Planificación Ambiental , Temperatura , Ciudades/epidemiología , Alemania/epidemiología , Trastornos de Estrés por Calor/epidemiología , Humanos , Humedad , Modelos Teóricos , Portugal/epidemiología , Luz Solar , Suecia/epidemiología
9.
Blood ; 124(13): 2142-9, 2014 Sep 25.
Artículo en Inglés | MEDLINE | ID: mdl-25139353

RESUMEN

Thrombotic microangiopathy (TMA) commonly involves injury of kidney glomerular endothelial cells (ECs) and fibrin occlusion of the capillaries. The mechanisms underlying repair of the microvasculature and recovery of kidney function are poorly defined. In the developing vasculature, the phosphoinositide 3-kinase (PI3K) α isoform integrates many growth factor cues. However, the role of individual isoforms in repair of the established vasculature is unclear. We found that postnatal endothelial deletion of PI3Kß sensitizes mice to lethal acute kidney failure after TMA injury. In vitro, PI3Kß-deficient ECs show reduced angiogenic invasion of fibrin matrix with unaltered sensitivity to proapoptotic stress compared with wild-type ECs. This correlates with decreased expression of the EC tip cell markers apelin and Dll4 and is associated with a reduction in migration and proliferation. In vivo, PI3Kß-knockdown ECs are deficient in assembly of microvessel-like structures. These data identify a critical role for endothelial PI3Kß in microvascular repair following injury.


Asunto(s)
Fosfatidilinositol 3-Quinasas Clase II/metabolismo , Endotelio Vascular/metabolismo , Endotelio Vascular/patología , Microvasos/metabolismo , Microvasos/patología , Microangiopatías Trombóticas/metabolismo , Microangiopatías Trombóticas/patología , Animales , Apoptosis/genética , Biomarcadores , Fosfatidilinositol 3-Quinasas Clase II/deficiencia , Fosfatidilinositol 3-Quinasas Clase II/genética , Modelos Animales de Enfermedad , Células Endoteliales/metabolismo , Activación Enzimática , Humanos , Glomérulos Renales/efectos de los fármacos , Glomérulos Renales/metabolismo , Glomérulos Renales/patología , Ratones , Ratones Noqueados , Fosfohidrolasa PTEN/metabolismo , Fosforilación/efectos de los fármacos , Proteínas Proto-Oncogénicas c-akt/metabolismo , Microangiopatías Trombóticas/genética , Microangiopatías Trombóticas/mortalidad , Factor A de Crecimiento Endotelial Vascular/farmacología
10.
Int J Biometeorol ; 58(5): 613-27, 2014 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-23456372

RESUMEN

Knowledge of how the mean radiant temperature (T mrt ) is affected by factors such as location, climate and urban setting contributes to the practice of climate sensitive planning. This paper examines how T mrt varies within an urban setting and how it is influenced by cloudiness. In addition, variations of T mrt in three high latitude cities are investigated in order to analyse the impact of geographical context and climate conditions. Results showed large spatial variations between sunlit and shaded areas during clear weather conditions, with the highest values of T mrt close to sunlit walls and the lowest values in the areas shaded by buildings and vegetation. As cloudiness increases, the spatial pattern is altered and the differences are reduced. The highest T mrt under cloudy conditions is instead found in open areas where the proportion of shortwave diffuse radiation from the sky vault is high. A regional comparison between three Swedish coastal cities showed that T mrt during summer is similar regardless of latitudinal location. On the other hand, large differences in T mrt during winter were found. Shadows, both from buildings and vegetation are the most effective measure to reduce extreme values of T mrt. However, extensive areas of shadow are usually not desired within outdoor urban environments at high latitude cities. One solution is to create diverse outdoor urban spaces in terms of shadow and also ventilation. This would provide individuals with access to a choice of thermal environments which they can use to assist their thermal regulation, based on personal needs and desires.


Asunto(s)
Ciudades , Modelos Teóricos , Luz Solar , Temperatura , Clima , Estaciones del Año , Análisis Espacial , Suecia
11.
PLoS One ; 8(10): e78244, 2013.
Artículo en Inglés | MEDLINE | ID: mdl-24143262

RESUMEN

The microvascular endothelium of the kidney glomerulus is injured in Shiga-like toxigenic bacterial infection, genetic or acquired loss of complement regulatory protein function, and allo-immune responses of solid-organ or bone marrow transplantation. Existing models of diseases with glomerular endothelial cell (EC) injury, collectively grouped as thrombotic microangiopathies, are problematic, impeding investigation of the mechanisms of microvascular defense and repair. To develop a model of glomerular endothelial injury in the mouse, we conjugated the M. oreades lectin to the cytotoxin, saporin, (LS) to selectively injure the glomerular endothelium. Injury of the microvasculature was evaluated by light, immunofluorescence, and electron microscopy, and by quantitative RT-PCR of cell-type specific transcripts. Renal function was evaluated by quantitation of serum creatinine. The toxin conjugate induced apoptosis of microvascular ECs in vitro, and subtle histologic features of thrombotic microangiopathy in vivo that were enhanced by co-injection of 50 µg/kg LPS. Among LS/LPS-treated animals, loss of glomerular EC staining correlated with decreased expression of EC-specific transcripts, and impaired kidney function. Selective injury of the glomerular microvasculature with LS toxin conjugate and LPS elicits histologic features of thrombotic microangiopathy and acute kidney failure.


Asunto(s)
Endotelio Vascular/lesiones , Glomérulos Renales/irrigación sanguínea , Animales , Apoptosis , Modelos Animales de Enfermedad , Endotelio Vascular/microbiología , Endotelio Vascular/patología , Femenino , Fibrina/metabolismo , Glomérulos Renales/patología , Glomérulos Renales/fisiopatología , Ratones , Microvasos/patología , Insuficiencia Renal/complicaciones , Trombosis/complicaciones
12.
J Phys Chem A ; 117(34): 8230-7, 2013 Aug 29.
Artículo en Inglés | MEDLINE | ID: mdl-23902565

RESUMEN

The reactions of small cationic platinum clusters (Pt2(+)-Pt7(+)) with molecular hydrogen were investigated, and the structures of the hydride complexes were analyzed using IR spectroscopy. We determined the relative reaction rates for the addition of the first H2 molecule to the platinum clusters, and we report the hydrogen saturation coverages observed at high H2 concentration. High H atom per Pt atom ratios were observed, similar to earlier measurements on other group-10 transition metals. The structures of the fully saturated complexes of Pt2(+)-Pt5(+) were investigated using a combination of infrared multiple-photon dissociation (IR-MPD) spectroscopy in the frequency range of 550-2050 cm(-1) and density functional theory-based calculations. We found molecularly bound hydrogen alongside bridge and often atop binding of hydrogen atoms for all of the low-energy structures, in contrast to earlier theoretical predictions.

13.
Pediatr Res ; 73(4 Pt 1): 435-42, 2013 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-23344679

RESUMEN

BACKGROUND: When asphyxiated neonates require additional cardiovascular support to moderate doses of dopamine infusion, controversy exists on the differential hemodynamic effects of two approaches (adding a second inotrope vs. increasing dopamine dosage). We hypothesized that high-dose dopamine (HD) would be detrimental to systemic and regional perfusion as compared with dopamine and epinephrine (D + E) combination therapy using a swine model of neonatal hypoxia-reoxygenation (H-R). METHODS: Twenty-seven piglets (1-4 d, 1.5-2.5 kg) were used for continuous monitoring of systemic arterial pressure (mean arterial pressure, MAP) and pulmonary arterial pressure (PAP), cardiac output (cardiac index, CI), and carotid (carotid artery flow index, CAFI), superior mesenteric (superior mesenteric artery flow index), and renal arterial flows. H-R piglets underwent 2 h of hypoxia followed by 2 h of reoxygenation before drug infusion (2 h). RESULTS: The hemodynamics of H-R piglets deteriorated gradually after reoxygenation. HD and D + E infusions improved CI similarly (both groups vs. control; P < 0.05). Both regimens increased MAP (P < 0.05) but not PAP, with decreased PAP/MAP ratio in D + E piglets. Both regimens improved CAFI and superior mesenteric artery flow index, with decreased mesenteric vascular resistance in HD-treated piglets. No significant effect on renal perfusion was observed. CONCLUSION: In H-R newborn piglets treated with a moderate dose of dopamine, adding epinephrine or further increasing dopamine improved systemic hemodynamics similarly; these treatments have differential effects on the pulmonary and mesenteric circulations.


Asunto(s)
Asfixia Neonatal/terapia , Cardiotónicos/administración & dosificación , Dopamina/administración & dosificación , Epinefrina/administración & dosificación , Hemodinámica/efectos de los fármacos , Resucitación , Animales , Animales Recién Nacidos , Presión Arterial/efectos de los fármacos , Asfixia Neonatal/sangre , Asfixia Neonatal/tratamiento farmacológico , Asfixia Neonatal/fisiopatología , Biomarcadores/sangre , Gasto Cardíaco/efectos de los fármacos , Arterias Carótidas/efectos de los fármacos , Arterias Carótidas/fisiopatología , Modelos Animales de Enfermedad , Quimioterapia Combinada , Humanos , Hipotensión/fisiopatología , Hipotensión/terapia , Recién Nacido , Oxígeno/sangre , Arteria Pulmonar/efectos de los fármacos , Arteria Pulmonar/fisiopatología , Circulación Renal/efectos de los fármacos , Choque Cardiogénico/fisiopatología , Choque Cardiogénico/terapia , Circulación Esplácnica/efectos de los fármacos , Porcinos , Factores de Tiempo , Troponina/sangre , Resistencia Vascular/efectos de los fármacos
14.
Anal Chem ; 84(13): 5633-40, 2012 Jul 03.
Artículo en Inglés | MEDLINE | ID: mdl-22670784

RESUMEN

We describe a novel ion source for analytical mass spectrometry based on femtosecond laser ionization at pressures at and above atmospheric and characterize its performance when coupled to a tandem quadrupole/time-of-flight mass spectrometer. We assess source saturation limits, ionization and sampling efficiencies, the effective ionization volume, and limits of detection. We demonstrate 100% efficient ionization for a set of organic compounds and show that the degree of ion fragmentation over a range of laser powers is favorable compared to electron impact ionization, especially in that a substantial parent ion signal is always observed. We show how collisional cooling plays a role in controlling fragmentation at high pressures and address how ion-molecule chemistry can be controlled or exploited. High-pressure femtosecond laser ionization will allow "universal" and efficient ionization, presenting a research direction that will broaden the options for gas phase analysis beyond the capabilities of electron impact ionization.

15.
J Chem Phys ; 136(21): 211103, 2012 Jun 07.
Artículo en Inglés | MEDLINE | ID: mdl-22697522

RESUMEN

The structures of small platinum clusters Pt(3-5)(+) are determined using far-infrared multiple photon dissociation spectroscopy of their argon complexes combined with density functional theory calculations. The clusters are found to have compact structures, and Pt(4)(+) and Pt(5)(+) already favor three-dimensional geometries, in contrast to a number of earlier predictions. Challenges in applying density functional theory to 3rd row transition metal clusters are addressed. Preliminary calculations suggest that the effects of spin-orbit coupling do not change the favoured lowest-energy isomers.

16.
J Chem Phys ; 131(18): 184706, 2009 Nov 14.
Artículo en Inglés | MEDLINE | ID: mdl-19916622

RESUMEN

The binding of carbon monoxide to iron, ruthenium, rhenium, and tungsten clusters is studied by means of infrared multiple photon dissociation spectroscopy. The CO stretching mode is used to probe the interaction of the CO molecule with the metal clusters and thereby the activation of the C-O bond. CO is found to adsorb molecularly to atop positions on iron clusters. On ruthenium and rhenium clusters it also binds molecularly. In the case of ruthenium, binding is predominantly to atop sites, however higher coordinated CO binding is also observed for both metals and becomes prevalent for rhenium clusters containing more than nine atoms. Tungsten clusters exhibit a clear size dependence for molecular versus dissociative CO binding. This behavior denotes the crossover to the purely dissociative CO binding on the earlier transition metals such as tantalum.

17.
J Leukoc Biol ; 86(1): 41-51, 2009 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-19383625

RESUMEN

The novel coinhibitory receptor BTLA may have a regulatory role in maintaining peripheral tolerance; however, its role in autoimmune diabetes is unknown. In this study, we show that anti-BTLA mAb 6F7 selectively depleted pathogenic B and CD4+ T(H) cells; enhanced the proportion of cells with the forkhead box p3+ PD-1+CD4+ regulatory T phenotype; and increased the production of potentially protective (IL-10) and detrimental (IL-2, IFN-gamma) cytokines in NOD mice. As interactions between BTLA and PD-1 coinhibitory pathways have been described in the cardiac allograft model, we also investigated if these pathways may have significant interaction in autoimmune diabetes. Anti-BTLA inhibited anti-PD-1-potentiated total IL-12 (p40+p70) production, suggesting the possibility that anti-BTLA may have a greater effect in the setting of anti-PD-1-triggered diabetes. To test this, NOD mice at 4 and 10 weeks of age were treated with anti-BTLA mAb, anti-PD-1 mAb, both mAb, or isotype control and were monitored for diabetes development. Although anti-BTLA mAb delayed diabetes onset significantly in 10- but not 4-week-old NOD mice, anti-BTLA mAb attenuated anti-PD-1-induced diabetes in both age groups. Hence, strategies targeting BTLA+ lymphocytes or therapies enhancing the BTLA-negative cosignal may prove valuable in treating autoimmune diabetes.


Asunto(s)
Anticuerpos Monoclonales/farmacología , Diabetes Mellitus Experimental/tratamiento farmacológico , Diabetes Mellitus Experimental/inmunología , Linfocitos/efectos de los fármacos , Receptores Inmunológicos/fisiología , Animales , Anticuerpos Monoclonales/administración & dosificación , Antígenos de Diferenciación/inmunología , Linfocitos B/patología , Linfocitos T CD4-Positivos/patología , Diabetes Mellitus Experimental/inducido químicamente , Interacciones Farmacológicas , Inmunofenotipificación , Interleucina-10/biosíntesis , Interleucina-12/biosíntesis , Recuento de Linfocitos , Ratones , Ratones Endogámicos NOD , Receptor de Muerte Celular Programada 1 , Receptores Inmunológicos/inmunología
19.
Phys Chem Chem Phys ; 10(40): 6144-9, 2008 Oct 28.
Artículo en Inglés | MEDLINE | ID: mdl-18846304

RESUMEN

The adsorption of a single CO molecule on clusters of the Group 10 transition metals is characterized by infrared multiple photon dissociation (IR-MPD) spectroscopy. The cationic, neutral, and anionic carbonyl complexes contain between 3 and up to 25 metal atoms. The C-O stretching frequency nu(CO) shows that while both nickel and platinum clusters adsorb CO only in atop positions, palladium clusters exhibit a variety of binding sites. These findings can be rationalized by considering the increasing role relativistic effects play in the electronic structure of the cluster complexes going down the group. Conclusions for the cluster-support interactions for size-selected supported particles are drawn from the charge dependence of nu(CO) for the gas-phase species.

20.
Science ; 321(5889): 674-6, 2008 Aug 01.
Artículo en Inglés | MEDLINE | ID: mdl-18669858

RESUMEN

The catalytic properties of gold nanoparticles are determined by their electronic and geometric structures. We revealed the geometries of several small neutral gold clusters in the gas phase by using vibrational spectroscopy between 47 and 220 wavenumbers. A two-dimensional structure for neutral Au7 and a pyramidal structure for neutral Au20 can be unambiguously assigned. The reduction of the symmetry when a corner atom is cut from the tetrahedral Au20 cluster is directly reflected in the vibrational spectrum of Au19.

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