Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 19 de 19
Filtrar
1.
Eur Arch Otorhinolaryngol ; 281(3): 1457-1462, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38183453

RESUMO

PURPOSE: To examine the role of the silicone stent in palliation of malignant central airway obstruction and identify potential preprocedural predictors for postprocedural outcome. METHODS: Patients treated with endoscopic insertion of tracheobronchial silicone stents for malignant central airway obstruction at Aarhus University Hospital from 2012 to 2022 were identified from electronic medical records. Statistical analyses were carried out to identify factors affecting Days Alive and Out of Hospital, complications and overall survival. RESULTS: 81 patients underwent a total of 90 tracheobronchial stent insertions. Days Alive and Out of Hospital (DAOH) for the first 30 days were affected negatively by urgent intervention, p < 0.001, preprocedural non-invasive respiratory support, p < 0.001, and preprocedural intubation, p = 0.02. Post-procedural oncological treatment was associated with a significant improved DAOH, p = 0.04. Symptomatology and lesion characteristics were not significantly associated with any impact on DAOH. Overall survival was poor (mean survival was 158 days), and only significantly affected by severe degree of dyspnea, p = 0.02, and postprocedural oncological treatment, p < 0.001. Complication where registered in 25.6% of cases within the first 30 days was observed. Procedure-related mortality was 3.7%. Based on chart annotations by an ENT-surgeon, 95% of the patients experienced relief of symptoms following stent insertion. CONCLUSIONS: Palliative tracheobronchial airway stenting with silicone stents is found to have a beneficial impact, more research is required for identification of predictors for postprocedural outcome based on preprocedural classifications.


Assuntos
Obstrução das Vias Respiratórias , Silicones , Humanos , Resultado do Tratamento , Obstrução das Vias Respiratórias/etiologia , Obstrução das Vias Respiratórias/cirurgia , Stents/efeitos adversos , Cuidados Paliativos , Broncoscopia
2.
Eur Arch Otorhinolaryngol ; 278(10): 4091-4099, 2021 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-33855628

RESUMO

PURPOSE: SARS-CoV-2 vaccines are a key step in fighting the pandemic. Nevertheless, their rapid development did not allow for testing among specific population subgroups such as pregnant and breastfeeding women, or elaborating specific guidelines for healthcare personnel working in high infection risk specialties, such as otolaryngology (ORL). This clinical consensus statement (CCS) aims to offer guidance for SARS-CoV-2 vaccination to this high-risk population based on the best evidence available. METHODS: A multidisciplinary international panel of 33 specialists judged statements through a two-round modified Delphi method survey. Statements were designed to encompass the following topics: risk of SARS-Cov-2 infection and use of protective equipment in ORL; SARS-Cov-2 infection and vaccines and respective risks for the mother/child dyad; and counseling for SARS-CoV-2 vaccination in pregnant, breastfeeding, or fertile healthcare workers (PBFHW). All ORL PBFHW were considered as the target audience. RESULTS: Of the 13 statements, 7 reached consensus or strong consensus, 2 reached no consensus, and 2 reached near-consensus. According to the statements with strong consensus otorhinolaryngologists-head and neck surgeons who are pregnant, breastfeeding, or with childbearing potential should have the opportunity to receive SARS-Cov-2 vaccination. Moreover, personal protective equipment (PPE) should still be used even after the vaccination. CONCLUSION: Until prospective evaluations on these topics are available, ORL-HNS must be considered a high infection risk specialty. While the use of PPE remains pivotal, ORL PBFHW should be allowed access to SARS-CoV-2 vaccination provided they receive up-to-date information.


Assuntos
Vacinas contra COVID-19 , COVID-19 , Otorrinolaringologistas , Cirurgiões , Aleitamento Materno , Consenso , Feminino , Humanos , Masculino , Gravidez , SARS-CoV-2 , Vacinação
3.
J Synchrotron Radiat ; 28(Pt 1): 131-145, 2021 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-33399562

RESUMO

In this paper the back-side-illuminated Percival 2-Megapixel (P2M) detector is presented, along with its characterization by means of optical and X-ray photons. For the first time, the response of the system to soft X-rays (250 eV to 1 keV) is presented. The main performance parameters of the first detector are measured, assessing the capabilities in terms of noise, dynamic range and single-photon discrimination capability. Present limitations and coming improvements are discussed.

4.
J Synchrotron Radiat ; 26(Pt 1): 253-262, 2019 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-30655493

RESUMO

Systematic studies of the performance of a water-cooled X-ray monochromator, designed and built for the B16 Test beamline at the Diamond Light Source, UK, are presented. A technical description of the monochromator is given and the results of commissioning measurements are discussed. Overall, the monochromator satisfies the original specifications well and meets all the major requirements of the versatile beamline. Following its successful implementation on B16, the basic monochromator design has been reproduced and adapted on other Diamond Light Source beamlines, including B18 and B21.

5.
Eur Arch Otorhinolaryngol ; 275(4): 847, 2018 04.
Artigo em Inglês | MEDLINE | ID: mdl-29488005
6.
Geospat Health ; 12(1): 505, 2017 05 08.
Artigo em Inglês | MEDLINE | ID: mdl-28555471

RESUMO

Temperature, precipitation and humidity are known to be important factors for the development of schistosome parasites as well as their intermediate snail hosts. Climate therefore plays an important role in determining the geographical distribution of schistosomiasis and it is expected that climate change will alter distribution and transmission patterns. Reliable predictions of distribution changes and likely transmission scenarios are key to efficient schistosomiasis intervention-planning. However, it is often difficult to assess the direction and magnitude of the impact on schistosomiasis induced by climate change, as well as the temporal transferability and predictive accuracy of the models, as prevalence data is often only available from one point in time. We evaluated potential climate-induced changes on the geographical distribution of schistosomiasis in Zimbabwe using prevalence data from two points in time, 29 years apart; to our knowledge, this is the first study investigating this over such a long time period. We applied historical weather data and matched prevalence data of two schistosome species (Schistosoma haematobium and S. mansoni). For each time period studied, a Bayesian geostatistical model was fitted to a range of climatic, environmental and other potential risk factors to identify significant predictors that could help us to obtain spatially explicit schistosomiasis risk estimates for Zimbabwe. The observed general downward trend in schistosomiasis prevalence for Zimbabwe from 1981 and the period preceding a survey and control campaign in 2010 parallels a shift towards a drier and warmer climate. However, a statistically significant relationship between climate change and the change in prevalence could not be established.


Assuntos
Mudança Climática , Esquistossomose/epidemiologia , Animais , Teorema de Bayes , Humanos , Schistosoma mansoni , Zimbábue/epidemiologia
7.
Risk Anal ; 36(3): 450-60, 2016 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-26856391

RESUMO

The aim of the project as the cluster analysis was to in part to develop a generic structured quantitative microbiological risk assessment (QMRA) model of human salmonellosis due to pork consumption in EU member states (MSs), and the objective of the cluster analysis was to group the EU MSs according to the relative contribution of different pathways of Salmonella in the farm-to-consumption chain of pork products. In the development of the model, by selecting a case study MS from each cluster the model was developed to represent different aspects of pig production, pork production, and consumption of pork products across EU states. The objective of the cluster analysis was to aggregate MSs into groups of countries with similar importance of different pathways of Salmonella in the farm-to-consumption chain using available, and where possible, universal register data related to the pork production and consumption in each country. Based on MS-specific information about distribution of (i) small and large farms, (ii) small and large slaughterhouses, (iii) amount of pork meat consumed, and (iv) amount of sausages consumed we used nonhierarchical and hierarchical cluster analysis to group the MSs. The cluster solutions were validated internally using statistic measures and externally by comparing the clustered MSs with an estimated human incidence of salmonellosis due to pork products in the MSs. Finally, each cluster was characterized qualitatively using the centroids of the clusters.


Assuntos
Microbiologia de Alimentos , Medição de Risco/métodos , Intoxicação Alimentar por Salmonella/prevenção & controle , Intoxicação Alimentar por Salmonella/transmissão , Salmonelose Animal/transmissão , Algoritmos , Animais , Análise por Conglomerados , União Europeia , Fazendas , Cadeia Alimentar , Humanos , Produtos da Carne/microbiologia , Modelos Estatísticos , Carne Vermelha/microbiologia , Reprodutibilidade dos Testes , Salmonella , Suínos/microbiologia
8.
J Synchrotron Radiat ; 23(1): 111-7, 2016 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-26698052

RESUMO

With the increased brilliance of state-of-the-art synchrotron radiation sources and the advent of free-electron lasers (FELs) enabling revolutionary science with EUV to X-ray photons comes an urgent need for suitable photon imaging detectors. Requirements include high frame rates, very large dynamic range, single-photon sensitivity with low probability of false positives and (multi)-megapixels. At DESY, one ongoing development project - in collaboration with RAL/STFC, Elettra Sincrotrone Trieste, Diamond, and Pohang Accelerator Laboratory - is the CMOS-based soft X-ray imager PERCIVAL. PERCIVAL is a monolithic active-pixel sensor back-thinned to access its primary energy range of 250 eV to 1 keV with target efficiencies above 90%. According to preliminary specifications, the roughly 10 cm × 10 cm, 3.5k × 3.7k monolithic sensor will operate at frame rates up to 120 Hz (commensurate with most FELs) and use multiple gains within 27 µm pixels to measure 1 to ∼100000 (500 eV) simultaneously arriving photons. DESY is also leading the development of the AGIPD, a high-speed detector based on hybrid pixel technology intended for use at the European XFEL. This system is being developed in collaboration with PSI, University of Hamburg, and University of Bonn. The AGIPD allows single-pulse imaging at 4.5 MHz frame rate into a 352-frame buffer, with a dynamic range allowing single-photon detection and detection of more than 10000 photons at 12.4 keV in the same image. Modules of 65k pixels each are configured to make up (multi)megapixel cameras. This review describes the AGIPD and the PERCIVAL concepts and systems, including some recent results and a summary of their current status. It also gives a short overview over other FEL-relevant developments where the Photon Science Detector Group at DESY is involved.

9.
J Synchrotron Radiat ; 22(3): 828-38, 2015 May.
Artigo em Inglês | MEDLINE | ID: mdl-25931103

RESUMO

I12 is the Joint Engineering, Environmental and Processing (JEEP) beamline, constructed during Phase II of the Diamond Light Source. I12 is located on a short (5 m) straight section of the Diamond storage ring and uses a 4.2 T superconducting wiggler to provide polychromatic and monochromatic X-rays in the energy range 50-150 keV. The beam energy enables good penetration through large or dense samples, combined with a large beam size (1 mrad horizontally × 0.3 mrad vertically). The beam characteristics permit the study of materials and processes inside environmental chambers without unacceptable attenuation of the beam and without the need to use sample sizes which are atypically small for the process under study. X-ray techniques available to users are radiography, tomography, energy-dispersive diffraction, monochromatic and white-beam two-dimensional diffraction/scattering and small-angle X-ray scattering. Since commencing operations in November 2009, I12 has established a broad user community in materials science and processing, chemical processing, biomedical engineering, civil engineering, environmental science, palaeontology and physics.


Assuntos
Cristalografia por Raios X/instrumentação , Lasers , Aceleradores de Partículas/instrumentação , Espectrometria por Raios X/instrumentação , Raios X , Transferência de Energia , Desenho de Equipamento , Análise de Falha de Equipamento , Iluminação/instrumentação , Reino Unido
10.
Parasit Vectors ; 7: 536, 2014 Dec 12.
Artigo em Inglês | MEDLINE | ID: mdl-25498001

RESUMO

BACKGROUND: Freshwater snails are intermediate hosts for a number of trematodes of which some are of medical and veterinary importance. The trematodes rely on specific species of snails to complete their life cycle; hence the ecology of the snails is a key element in transmission of the parasites. More than 200 million people are infected with schistosomes of which 95% live in sub-Saharan Africa and many more are living in areas where transmission is on-going. Human infection with the Fasciola parasite, usually considered more of veterinary concern, has recently been recognised as a human health problem. Many countries have implemented health programmes to reduce morbidity and prevalence of schistosomiasis, and control programmes to mitigate food-borne fascioliasis. As these programmes are resource demanding, baseline information on disease prevalence and distribution becomes of great importance. Such information can be made available and put into practice through maps depicting spatial distribution of the intermediate snail hosts. METHODS: A biology driven model for the freshwater snails Bulinus globosus, Biomphalaria pfeifferi and Lymnaea natalensis was used to make predictions of snail habitat suitability by including potential underlying environmental and climatic drivers. The snail observation data originated from a nationwide survey in Zimbabwe and the prediction model was parameterised with a high resolution Regional Climate Model. Georeferenced prevalence data on urinary and intestinal schistosomiasis and fascioliasis was used to calibrate the snail habitat suitability predictions to produce binary maps of snail presence and absence. RESULTS: Predicted snail habitat suitability across Zimbabwe, as well as the spatial distribution of snails, is reported for three time slices representative for present (1980-1999) and future climate (2046-2065 and 2080-2099). CONCLUSIONS: It is shown from the current study that snail habitat suitability is highly variable in Zimbabwe, with distinct high- and low- suitability areas and that temperature may be the main driving factor. It is concluded that future climate change in Zimbabwe may cause a reduced spatial distribution of suitable habitat of host snails with a probable exception of Bi. pfeifferi, the intermediate host for intestinal schistosomiasis that may increase around 2055 before declining towards 2100.


Assuntos
Distribuição Animal , Mudança Climática , Modelos Biológicos , Caramujos/parasitologia , Trematódeos/fisiologia , Animais , Ecossistema , Interações Hospedeiro-Parasita , Caramujos/fisiologia , Zimbábue , Zoonoses
11.
Geospat Health ; 8(2): 335-43, 2014 May.
Artigo em Inglês | MEDLINE | ID: mdl-24893011

RESUMO

The environment, the on-going global climate change and the ecology of animal species determine the localisation of habitats and the geographical distribution of the various species in nature. The aim of this study was to explore the effects of such changes on snail species not only of interest to naturalists but also of importance to human and animal health. The spatial distribution of freshwater snail intermediate hosts involved in the transmission of schistosomiasis, fascioliasis and paramphistomiasis (i.e. Bulinus globosus, Biomphalaria pfeifferi and Lymnaea natalensis) were modelled by the use of a maximum entropy algorithm (Maxent). Two snail observation datasets from Zimbabwe, from 1988 and 2012, were compared in terms of geospatial distribution and potential distributional change over this 24-year period investigated. Climate data, from the two years were identified and used in a species distribution modelling framework to produce maps of predicted suitable snail habitats. Having both climate- and snail observation data spaced 24 years in time represent a unique opportunity to evaluate biological response of snails to changes in climate variables. The study shows that snail habitat suitability is highly variable in Zimbabwe with foci mainly in the central Highveld but also in areas to the South and West. It is further demonstrated that the spatial distribution of suitable habitats changes with variation in the climatic conditions, and that this parallels that of the predicted climate change.


Assuntos
Mudança Climática , Fasciolíase/epidemiologia , Esquistossomose/epidemiologia , Caramujos/parasitologia , Algoritmos , Animais , Fasciolíase/transmissão , Humanos , Modelos Teóricos , Esquistossomose/transmissão , Análise Espacial , Infecções por Trematódeos/epidemiologia , Infecções por Trematódeos/transmissão , Zimbábue/epidemiologia
12.
Ugeskr Laeger ; 172(17): 1289-93, 2010 Apr 26.
Artigo em Dinamarquês | MEDLINE | ID: mdl-20444396

RESUMO

INTRODUCTION: Surgical treatment of tracheal stenoses (TS) using tracheal resection (TR) is a treatment modality that should be considered in every case. We report the results from TR in a consecutive series of 17 patients in Western Denmark during the past five years. MATERIAL AND METHODS: A total of 32 patients with TS were retrospectively evaluated, of whom 17 underwent TR with end-to-end anastomoses. Age, gender, aetiology, symptoms, findings, localisation and length of the stenoses were registered. In addition, other procedures than TR and patient satisfaction were registered. RESULTS: Nine (53%) and three (18%) had post-tracheostomy and post-intubation stenoses, three (18%) had an intraluminal tumour, two (12%) had amyloidosis and sequelae after fracture of a tracheal ring, respectively. Prior to surgery, 29% underwent stent implantation, 41 and 47%, respectively, had had laser resection and/or dilation a number of times. The median stenosis length was 1.1 cm (0.4-2.0 cm), and they were primarily located 2-4 cm below the vocal cords. The length of resection ranged from 2.0 to 3.5 cm (median 2.3). Postoperatively, one (5.8%) patient died and one needed reoperation due to haematoma, none developed insufficient anastomosis and of those with preoperative permanent tracheal tube, all but one could do without the tube after surgery. The follow-up period was 3.0 years (0.0-5.5 yrs). 75% was - according to questionnaire answers - very satisfied with the result, 25% were moderately satisfied. CONCLUSION: The results from surgical treatment of TS in Denmark are in line with international studies and TR is the treatment of choice in selected patients with TS.


Assuntos
Estenose Traqueal/cirurgia , Adolescente , Adulto , Idoso , Pré-Escolar , Feminino , Seguimentos , Humanos , Masculino , Pessoa de Meia-Idade , Satisfação do Paciente , Sistema de Registros , Reoperação , Estudos Retrospectivos , Inquéritos e Questionários , Estenose Traqueal/diagnóstico , Estenose Traqueal/etiologia , Resultado do Tratamento , Adulto Jovem
13.
Eur Arch Otorhinolaryngol ; 266(12): 1945-52, 2009 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-19301027

RESUMO

As bleeding in the neck region is a potentially life-threatening complication, we found it imperative to concretize the frequency and to identify possible reasons for this complication. A national database of all thyroid surgery performed inside the specialty of ENT Head and Neck Surgery (THYKIR) was established in January 2001. This nationwide cohort study represents 5,490 patients included until December 2007. Overall hemorrhage frequency was 4.2% with a wide variation among departments. Multiple regression analysis identified age, male gender, malignant histology and extent of surgery as independent risk factors for hemorrhage. Increased hospital stay and infection rates were found in patients treated with drainage. The median time for onset of postoperative hemorrhage was 3 h (range 0-105). Compared with international literature our incidence of post-thyroidectomy hemorrhage is relatively high. Improvement might be reached by the exchange of experience between departments with focus on adequate surgical technique and careful hemostasis.


Assuntos
Hemorragia Pós-Operatória/epidemiologia , Centros Cirúrgicos/estatística & dados numéricos , Doenças da Glândula Tireoide/cirurgia , Tireoidectomia/efeitos adversos , Adolescente , Adulto , Idoso , Idoso de 80 Anos ou mais , Criança , Pré-Escolar , Dinamarca/epidemiologia , Feminino , Seguimentos , Humanos , Incidência , Lactente , Recém-Nascido , Masculino , Pessoa de Meia-Idade , Hemorragia Pós-Operatória/etiologia , Prognóstico , Estudos Retrospectivos , Fatores de Risco , Fatores de Tempo , Adulto Jovem
14.
Acta Oncol ; 47(3): 451-7, 2008.
Artigo em Inglês | MEDLINE | ID: mdl-17906980

RESUMO

INTRODUCTION: Papillary microcarcinomas (PMC) of the thyroid gland are defined according to The WHO Committee as papillary carcinomas measuring 10 mm or less in diameter. A large proportion of these tumours are found coincidentally in the treatment of symptomatic goitre and most cases follow an indolent course with an excellent prognosis. However, a more aggressive behaviour with regional and distant metastases does occur. The aim of this study was to evaluate if the immunohistochemical markers cyclin D1 or galectin-3 might indicate the presence of metastatic disease in patients with PMC at the time of diagnosis. MATERIAL AND METHODS: From the 1(st) of January 1996 to 31(st) of December 2002 a total of 169 PMC patients were diagnosed and registered in the national Danish thyroid cancer database DATHYRCA and 131 of these were eligible for the study. Forty-three (33%) had histologically verified regional or distant metastases. Slides were cut from the primary tumour and immunostaining and quantification was subsequently performed. RESULTS: The percentage of positive cells was examined for patients with and without metastases. For cyclin D1 the median values were 31% (range: 0-59) and 21% (range: 0-75), respectively, showing a statistically significant difference (p=0.02). For galectin-3 the medians were 87% (range: 6-96) and 85% (range: 0-99) and no significant difference was found. CONCLUSION: Cyclin D1 showed significantly higher median expression in patients with metastases compared to those without, indicating a correlation to tumour aggressiveness. However, both groups showed large variation in expression, which disqualify the marker as a discriminator for the detection of metastases. Galectin-3 was without any significant correlation to the presence of metastases from PMC.


Assuntos
Biomarcadores Tumorais/análise , Carcinoma Papilar/secundário , Ciclinas/análise , Galectina 3/análise , Proteínas de Neoplasias/análise , Neoplasias da Glândula Tireoide/química , Adulto , Biomarcadores Tumorais/genética , Carcinoma Papilar/química , Carcinoma Papilar/epidemiologia , Carcinoma Papilar/genética , Ciclina D , Ciclinas/genética , Bases de Dados Factuais , Dinamarca/epidemiologia , Feminino , Galectina 3/genética , Regulação Neoplásica da Expressão Gênica , Humanos , Masculino , Pessoa de Meia-Idade , Proteínas de Neoplasias/genética , Neoplasias da Glândula Tireoide/epidemiologia , Neoplasias da Glândula Tireoide/genética , Neoplasias da Glândula Tireoide/patologia
15.
Am J Disaster Med ; 3(6): 327-33, 2008.
Artigo em Inglês | MEDLINE | ID: mdl-19202886

RESUMO

Human health threats posed by airborne pathogens are difficult to handle for healthcare responders due to the fact that the contaminated area is not immediately recognizable. By means of wind dispersion modeling, it is possible to estimate the extent and geographical position of hazardous areas and health impact. Contemporary modeling tools can run on standard PCs, with short processing time and with easy-to-use interfaces. This enables health professionals without modeling experience to assess consequences of dispersion incidents, for example, from accidental releases from industries, shedding of pathogens from infectious animals or humans, as well as intentional releases caused by terrorist activity. Dispersion assessments can provide response managers with a chance to get on top of events. In the absence of modeling, reliable estimates of hazard areas may not be available until no earlier than the appearance of the first cases or after time-consuming sampling and laboratory analysis. In this article, the authors describe the concept of using wind dispersion assessments in epidemiological field investigations of naturally occurring disease outbreaks, as well as for bioterror scenarios. They describe the specifications of user friendly and real-time functional wind dispersion modeling systems that can serve as decision support tools during outbreak investigations and outline some of the currently available software packages.


Assuntos
Poluentes Atmosféricos/análise , Técnicas de Apoio para a Decisão , Planejamento em Desastres/organização & administração , Surtos de Doenças/prevenção & controle , Animais , Bioterrorismo , Humanos , Legionelose/epidemiologia , Conceitos Meteorológicos , Febre Q/epidemiologia , Medição de Risco , Síndrome Respiratória Aguda Grave/epidemiologia , Vento
17.
Ugeskr Laeger ; 167(36): 3401-2, 2005 Sep 05.
Artigo em Dinamarquês | MEDLINE | ID: mdl-16159492

RESUMO

INTRODUCTION: Disease outbreak monitoring is relevant not only for naturally occurring diseases but also for detecting a biological terror event. Surveillance systems are already operational in Denmark, but none of these has the high update frequencies necessary for early warning, and the majority monitor specific infectious diseases. MATERIALS AND METHODS: An early-warning system for detection of disease outbreaks in Denmark based on ambulance transport frequency was developed and tested employing a biological outbreak scenario. RESULTS: The system, termed "Bioalarm", demonstrated an ability to adapt to minor statistical variations due to, e.g., mild influenza epidemics and at the same time to elicit an early warning in the event of a outbreak consistent with a bioterrorist attack. CONCLUSION: Bioalarm not only is relevant for early warning of a disease outbreak as a result of a biological attack but also facilitates early detection of naturally occurring outbreaks.


Assuntos
Ambulâncias/estatística & dados numéricos , Bioterrorismo , Planejamento em Desastres , Surtos de Doenças/estatística & dados numéricos , Sistemas de Comunicação entre Serviços de Emergência/estatística & dados numéricos , Vigilância da População/métodos , Bioterrorismo/prevenção & controle , Dinamarca/epidemiologia , Serviços Médicos de Emergência/estatística & dados numéricos , Humanos
18.
J Chem Phys ; 120(11): 5067-72, 2004 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-15267374

RESUMO

Lifetimes of triplet-state molecules and triplet quantum yields are important parameters in photobiology as they determine the generation of singlet-oxygen upon irradiation with visible light. Here we report lifetimes of protoporphyrin IX (pp) in vacuo measured in an ion storage ring. We find that after 532 nm photon absorption, pp(-) (free base and negatively charged carboxylate) and pp(+) (single protonation of ring nitrogen) have triplet-state lifetimes of 12 and 6 ms, respectively. After 415 or 390 nm absorption the lifetime of the anion is shorter (1.5 and 0.6 ms) as expected from the increase in temperature. Triplet quantum yields of pp(-) and pp(+) are similar, 0.6-0.7, close to values reported for the free base and monocation in solution. The other channel, direct decay to the electronic ground state and subsequent dissociation of vibrationally excited ions, is much faster than triplet-singlet intersystem crossing. We measured lifetimes of 63 micros, 96 micros, and 0.3 ms after 390, 415, and 532 nm excitation, respectively. A fit of a statistical model to the pp(-) decay results in an Arrhenius activation energy of 0.5+/-0.2 eV for CO(2) loss and a low preexponential factor (10(6)-10(10) s(-1)), indicative of an entropic barrier.


Assuntos
Luz , Protoporfirinas/química , Protoporfirinas/efeitos da radiação , Teoria Quântica , Absorção , Íons , Cinética , Modelos Estatísticos , Fótons , Oxigênio Singlete/química , Oxigênio Singlete/metabolismo , Termodinâmica
SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA
...