| 1. |
- Grosche, S, et al.
(författare)
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Rare variant analysis in eczema identifies exonic variants in DUSP1, NOTCH4 and SLC9A4
- 2021
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Ingår i: Nature communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 12:1, s. 6618-
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Tidskriftsartikel (refereegranskat)abstract
- Previous genome-wide association studies revealed multiple common variants involved in eczema but the role of rare variants remains to be elucidated. Here, we investigate the role of rare variants in eczema susceptibility. We meta-analyze 21 study populations including 20,016 eczema cases and 380,433 controls. Rare variants are imputed with high accuracy using large population-based reference panels. We identify rare exonic variants in DUSP1, NOTCH4, and SLC9A4 to be associated with eczema. In DUSP1 and NOTCH4 missense variants are predicted to impact conserved functional domains. In addition, five novel common variants at SATB1-AS1/KCNH8, TRIB1/LINC00861, ZBTB1, TBX21/OSBPL7, and CSF2RB are discovered. While genes prioritized based on rare variants are significantly up-regulated in the skin, common variants point to immune cell function. Over 20% of the single nucleotide variant-based heritability is attributable to rare and low-frequency variants. The identified rare/low-frequency variants located in functional protein domains point to promising targets for novel therapeutic approaches to eczema.
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| 9. |
- Lankester, Arjan C, et al.
(författare)
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Hematopoietic cell transplantation in severe combined immunodeficiency: The SCETIDE 2006-2014 European cohort.
- 2022
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Ingår i: The Journal of allergy and clinical immunology. - : Elsevier BV. - 1097-6825 .- 0091-6749. ; 149:5
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Tidskriftsartikel (refereegranskat)abstract
- Hematopoietic stem cell transplantation (HSCT) represents a curative treatment for patients with severe combined immunodeficiency (SCID), a group of monogenic immune disorders with an otherwise fatal outcome.We performed a comprehensive multicenter analysis of genotype-specific HSCT outcome, including detailed analysis of immune reconstitution (IR) and the predictive value for clinical outcome.HSCT outcome was studied in 338 patients with genetically confirmed SCID who underwent transplantation in 2006-2014 and who were registered in the SCETIDE registry. In a representative subgroup of 152 patients, data on IR and long-term clinical outcome were analyzed.Two-year OS was similar with matched family and unrelated donors and better than mismatched donor HSCT (P<.001). The 2-year event-free survival (EFS) was similar in matched and mismatched unrelated donor and less favorable in mismatched related donor (MMRD) HSCT (P< .001). Genetic subgroups did not differ in 2-year OS (P= .1) and EFS (P=.073). In multivariate analysis, pretransplantation infections and use of MMRDs were associated with less favorable OS and EFS. With a median follow-up of 6.2 years (range, 2.0-11.8 years), 73 of 152 patients in the IR cohort were alive and well without Ig dependency. IL-2 receptor gamma chain/Janus kinase 3/IL-7 receptor-deficient SCID, myeloablative conditioning, matched donor HSCT, and naive CD4 T lymphocytes >0.5×10e3/μL at+1 year were identified as independent predictors of favorable clinical and immunologic outcome.Recent advances in HSCT in SCID patients have resulted in improved OS and EFS in all genotypes and donor types. To achieve a favorable long-term outcome, treatment strategies should aim for optimal naive CD4 T lymphocyte regeneration.
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| 16. |
- Baptista, Marisa A. P., et al.
(författare)
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Deletion of Wiskott-Aldrich syndrome protein triggers Rac2 activity and increased cross-presentation by dendritic cells
- 2016
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 7
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Tidskriftsartikel (refereegranskat)abstract
- Wiskott-Aldrich syndrome (WAS) is caused by loss-of-function mutations in the WASp gene. Decreased cellular responses in WASp-deficient cells have been interpreted to mean that WASp directly regulates these responses in WASp-sufficient cells. Here, we identify an exception to this concept and show that WASp-deficient dendritic cells have increased activation of Rac2 that support cross-presentation to CD8(+) T cells. Using two different skin pathology models, WASp-deficient mice show an accumulation of dendritic cells in the skin and increased expansion of IFN gamma-producing CD8(+) T cells in the draining lymph node and spleen. Specific deletion of WASp in dendritic cells leads to marked expansion of CD8(+) T cells at the expense of CD4(+) T cells. WASp-deficient dendritic cells induce increased cross-presentation to CD8(+) T cells by activating Rac2 that maintains a near neutral pH of phagosomes. Our data reveals an intricate balance between activation of WASp and Rac2 signalling pathways in dendritic cells.
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| 17. |
- Devos, David, et al.
(författare)
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Trial of Deferiprone in Parkinson’s Disease
- 2022
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Ingår i: New England Journal of Medicine. - : Massachusetts Medical Society. - 0028-4793 .- 1533-4406. ; 387:22, s. 2045-2055
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Tidskriftsartikel (refereegranskat)abstract
- BACKGROUNDIron content is increased in the substantia nigra of persons with Parkinson's disease and may contribute to the pathophysiology of the disorder. Early research suggests that the iron chelator deferiprone can reduce nigrostriatal iron content in persons with Parkinson's disease, but its effects on disease progression are unclear.METHODSWe conducted a multicenter, phase 2, randomized, double-blind trial involving participants with newly diagnosed Parkinson's disease who had never received levodopa. Participants were assigned (in a 1:1 ratio) to receive oral deferiprone at a dose of 15 mg per kilogram of body weight twice daily or matched placebo for 36 weeks. Dopaminergic therapy was withheld unless deemed necessary for symptom control. The primary outcome was the change in the total score on the Movement Disorder Society-sponsored revision of the Unified Parkinson's Disease Rating Scale (MDS-UPDRS; range, 0 to 260, with higher scores indicating more severe impairment) at 36 weeks. Secondary and exploratory clinical outcomes at up to 40 weeks included measures of motor and nonmotor disability. Brain iron content measured with the use of magnetic resonance imaging was also an exploratory outcome.RESULTSA total of 372 participants were enrolled; 186 were assigned to receive deferiprone and 186 to receive placebo. Progression of symptoms led to the initiation of dopaminergic therapy in 22.0% of the participants in the deferiprone group and 2.7% of those in the placebo group. The mean MDS-UPDRS total score at baseline was 34.3 in the deferiprone group and 33.2 in the placebo group and increased (worsened) by 15.6 points and 6.3 points, respectively (difference, 9.3 points; 95% confidence interval, 6.3 to 12.2; P<0.001). Nigrostriatal iron content decreased more in the deferiprone group than in the placebo group. The main serious adverse events with deferiprone were agranulocytosis in 2 participants and neutropenia in 3 participants.CONCLUSIONSIn participants with early Parkinson's disease who had never received levodopa and in whom treatment with dopaminergic medications was not planned, deferiprone was associated with worse scores in measures of parkinsonism than those with placebo over a period of 36 weeks.
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| 18. |
- Jenkins, Andrew J., et al.
(författare)
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The Ehrenfest method with fully quantum nuclear motion (Qu-Eh) : Application to charge migration in radical cations
- 2018
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 149:9
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Tidskriftsartikel (refereegranskat)abstract
- An algorithm is described for quantum dynamics where an Ehrenfest potential is combined with fully quantum nuclear motion (Quantum-Ehrenfest, Qu-Eh). The method is related to the single-set variational multi-configuration Gaussian approach (vMCG) but has the advantage that only a single quantum chemistry computation is required at each time step since there is only a single time-dependent potential surface. Also shown is the close relationship to the “exact factorization method.” The quantum Ehrenfest method is compared with vMCG for study of electron dynamics in a modified bismethylene-adamantane cation system. Illustrative examples of electron-nuclear dynamics are presented for a distorted allene system and for HCCI+ where one has a degenerate Π system.
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| 19. |
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| 20. |
- Schuette, Moritz, et al.
(författare)
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Molecular dissection of colorectal cancer in pre-clinical models identifies biomarkers predicting sensitivity to EGFR inhibitors
- 2017
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 8
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Tidskriftsartikel (refereegranskat)abstract
- Colorectal carcinoma represents a heterogeneous entity, with only a fraction of the tumours responding to available therapies, requiring a better molecular understanding of the disease in precision oncology. To address this challenge, the OncoTrack consortium recruited 106 CRC patients (stages I-IV) and developed a pre-clinical platform generating a compendium of drug sensitivity data totalling 44,000 assays testing 16 clinical drugs on patient-derived in vivo and in vitro models. This large biobank of 106 tumours, 35 organoids and 59 xenografts, with extensive omics data comparing donor tumours and derived models provides a resource for advancing our understanding of CRC. Models recapitulate many of the genetic and transcriptomic features of the donors, but defined less complex molecular sub-groups because of the loss of human stroma. Linking molecular profiles with drug sensitivity patterns identifies novel biomarkers, including a signature outperforming RAS/RAF mutations in predicting sensitivity to the EGFR inhibitor cetuximab.
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| 21. |
- Spinlove, K. E., et al.
(författare)
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Using quantum dynamics simulations to follow the competition between charge migration and charge transfer in polyatomic molecules
- 2017
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Ingår i: Chemical Physics. - : ELSEVIER SCIENCE BV. - 0301-0104 .- 1873-4421. ; 482, s. 52-63
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Tidskriftsartikel (refereegranskat)abstract
- Recent work, particularly by Cederbaum and co-workers, has identified the phenomenon of charge migration, whereby charge flow occurs over a static molecular framework after the creation of an electronic wavepacket. In a real molecule, this charge migration competes with charge transfer, whereby the nuclear motion also results in the re-distribution of charge. To study this competition, quantum dynamics simulations need to be performed. To break the exponential scaling of standard grid-based algorithms, approximate methods need to be developed that are efficient yet able to follow the coupled electronic-nuclear motion of these systems. Using a simple model Hamiltonian based on the ionisation of the allene molecule, the performance of different methods based on Gaussian Wavepackets is demonstrated.
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| 24. |
- Blundell, MP, et al.
(författare)
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Phosphorylation of WASp is a key regulator of activity and stability in vivo
- 2009
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Ingår i: Proceedings of the National Academy of Sciences of the United States of America. - : Proceedings of the National Academy of Sciences. - 1091-6490. ; 106:37, s. 15738-15743
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Tidskriftsartikel (refereegranskat)abstract
- The Wiskott-Aldrich syndrome protein (WASp) is a key cytoskeletal regulator in hematopoietic cells. Covalent modification of a conserved tyrosine by phosphorylation has emerged as an important potential determinant of activity, although the physiological significance remains uncertain. In a murine knockin model, mutation resulting in inability to phosphorylate Y293 (Y293F) mimicked many features of complete WASp-deficiency. Although a phosphomimicking mutant Y293E conferred enhanced actin-polymerization, the cellular phenotype was similar due to functional dysregulation. Furthermore, steady-state levels of Y293E-WASp were markedly reduced compared to wild-type WASp and Y293F-WASp, although partially recoverable by treatment of cells with proteasome inhibitors. Consequently, tyrosine phosphorylation plays a critical role in normal activation of WASp in vivo, and is indispensible for multiple tasks including proliferation, phagocytosis, chemotaxis, and assembly of adhesion structures. Furthermore, it may target WASp for proteasome-mediated degradation, thereby providing a default mechanism for self-limiting stimulation of the Arp2/3 complex.
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| 26. |
- Helvig, Sanne de Jong, et al.
(författare)
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A comparison of lab-scale free rotating wind turbines and actuator disks
- 2021
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Ingår i: Journal of Wind Engineering and Industrial Aerodynamics. - : Elsevier BV. - 0167-6105 .- 1872-8197. ; 209
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Tidskriftsartikel (refereegranskat)abstract
- Planar particle image velocimetry was conducted upstream and in the near-wake of a lab-scale free-rotating wind turbine model and compared to several actuator disks with the same dimensions. The Reynolds number of the incoming flow is order 10(4). Actuator disks with different designs and solidities were tested, and the process of actuator disk selection is explicitly shown. The drag, mean velocity and mean vorticity in the wake of the disks were compared to that of the rotating model. For the disk that was the best match, the Reynolds stresses and swirling strength are also presented. The instantaneous swirling strength illustrated that despite similar mean fields, the instantaneous phenomena were significantly different. Distinct tip vortices were present in the wake of the rotating model but were absent from the wake of the actuator disk. Proper orthogonal decomposition was used to further investigate the underlying phenomena in the two flows, again demonstrating the importance of tip vortices when studying the rotating model and the lack of such distinct vortices when using the actuator disk. Hence, despite well-matched mean characteristics, the instantaneous structures in the two flows remain distinct.
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| 27. |
- Loarer, T., et al.
(författare)
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Fuel retention in L and H mode experiments in JET
- 2007
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Ingår i: 34th EPS Conference on Plasma Physics 2007, EPS 2007 - Europhysics Conference Abstracts. - 9781622763344 ; , s. 13-16
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Konferensbidrag (refereegranskat)abstract
- The fuel retention has been studied out in JET in L mode, Type III and Type I ELMy H-modes using gas balance in series of repetitive pulses with an overall accuracy of about 1.2%. The short term (dynamic) retention is important for both L mode and Type III ELMy H-mode over the heating phases (respectively 13 and 17 sec) but decreases already significantly during the pulse. It becomes small already after 6 sec for the Type I ELMy H-mode conditions. In all the cases, the recovery after the pulse contributes for a weak part in the gas balance and in the overall fuel retention. The absolute long term fuel retention (on the time basis of typically 5 hours) for the different plasma conditions is between 1.3 and 2.8 1021Ds-1 (averaged over the plasma heating time) and in reasonable agreement with the value deduced from post mortem tile analysis of about 5 1020Ds-1 considering the additional long term outgassing, conditioning and disruptions included in the post mortem analysis. The increase of the long term retention observed from L mode to Type I ELMy H-mode is associated to the increase of the recycling flux and the ELM energy. This larger long term retention is attributed to an enhanced carbon erosion and transport in the SOL leading to stronger carbon deposition and fuel codeposition. The results confirm the strong concerns about fuel retention in a carbon clad tokamak and a possible full carbon wall ITER which could reach the T-inventory limit in only a small number of high performance shots. A reasonable ITER operation time depends thus on a significant reduced T codeposition under the different ITER material conditions (which has to be confirmed in a relevant tokamak experiment such as the JET ILW project) and an effective routine T removal technique.
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| 28. |
- Maccari, Maria Elena, et al.
(författare)
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Activated phosphoinositide 3-kinase δ syndrome: Update from the ESID Registry and comparison with other autoimmune-lymphoproliferative inborn errors of immunity.
- 2023
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Ingår i: The Journal of allergy and clinical immunology. - 1097-6825. ; 152:4
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Tidskriftsartikel (refereegranskat)abstract
- Activated phosphoinositide-3-kinase δ syndrome (APDS) is an inborn error of immunity (IEI) with infection susceptibility and immune dysregulation, clinically overlapping with other conditions. Management depends on disease evolution, but predictors of severe disease are lacking.This study sought to report the extended spectrum of disease manifestations in APDS1 versus APDS2; compare these to CTLA4 deficiency, NFKB1 deficiency, and STAT3 gain-of-function (GOF) disease; and identify predictors of severity in APDS.Data was collected from the ESID (European Society for Immunodeficiencies)-APDS registry and was compared with published cohorts of the other IEIs.The analysis of 170 patients with APDS outlines high penetrance and early onset of APDS compared to the other IEIs. The large clinical heterogeneity even in individuals with the same PIK3CD variant E1021K illustrates how poorly the genotype predicts the disease phenotype and course. The high clinical overlap between APDS and the other investigated IEIs suggests relevant pathophysiological convergence of the affected pathways. Preferentially affected organ systems indicate specific pathophysiology: bronchiectasis is typical of APDS1; interstitial lung disease and enteropathy are more common in STAT3 GOF and CTLA4 deficiency. Endocrinopathies are most frequent in STAT3 GOF, but growth impairment is also common, particularly in APDS2. Early clinical presentation is a risk factor for severe disease in APDS.APDS illustrates how a single genetic variant can result in a diverse autoimmune-lymphoproliferative phenotype. Overlap with other IEIs is substantial. Some specific features distinguish APDS1 from APDS2. Early onset is a risk factor for severe disease course calling for specific treatment studies in younger patients.
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| 29. |
- Mansouri, Kamel, et al.
(författare)
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CERAPP : Collaborative Estrogen Receptor Activity Prediction Project
- 2016
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Ingår i: Journal of Environmental Health Perspectives. - : Environmental Health Perspectives. - 0091-6765 .- 1552-9924. ; 124:7, s. 1023-1033
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Tidskriftsartikel (refereegranskat)abstract
- BACKGROUND: Humans are exposed to thousands of man-made chemicals in the environment. Some chemicals mimic natural endocrine hormones and, thus, have the potential to be endocrine disruptors. Most of these chemicals have never been tested for their ability to interact with the estrogen receptor (ER). Risk assessors need tools to prioritize chemicals for evaluation in costly in vivo tests, for instance, within the U.S. EPA Endocrine Disruptor Screening Program. OBJECTIVES: We describe a large-scale modeling project called CERAPP (Collaborative Estrogen Receptor Activity Prediction Project) and demonstrate the efficacy of using predictive computational models trained on high-throughput screening data to evaluate thousands of chemicals for ER-related activity and prioritize them for further testing. METHODS: CERAPP combined multiple models developed in collaboration with 17 groups in the United States and Europe to predict ER activity of a common set of 32,464 chemical structures. Quantitative structure-activity relationship models and docking approaches were employed, mostly using a common training set of 1,677 chemical structures provided by the U.S. EPA, to build a total of 40 categorical and 8 continuous models for binding, agonist, and antagonist ER activity. All predictions were evaluated on a set of 7,522 chemicals curated from the literature. To overcome the limitations of single models, a consensus was built by weighting models on scores based on their evaluated accuracies. RESULTS: Individual model scores ranged from 0.69 to 0.85, showing high prediction reliabilities. Out of the 32,464 chemicals, the consensus model predicted 4,001 chemicals (12.3%) as high priority actives and 6,742 potential actives (20.8%) to be considered for further testing.CONCLUSION: This project demonstrated the possibility to screen large libraries of chemicals using a consensus of different in silico approaches. This concept will be applied in future projects related to other end points.
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| 30. |
- Stjerna, Marie-Louise, et al.
(författare)
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Risk as a relational phenomenon : a cross-cultural analysis of parents’ understandings of child food allergy and risk management
- 2017
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Ingår i: Health, Risk and Society. - : Routledge. - 1369-8575 .- 1469-8331. ; 19:7-8, s. 351-368
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Tidskriftsartikel (refereegranskat)abstract
- Western culture can be seen as permeated by risk-consciousness. In particular, parents are under scrutiny in their roles as risk managers. In this article, we address parental experiences of children more at risk than other children, children with food allergy, and the management of allergy risk in everyday life. Drawing on a notion of risk as ‘situated’ in local everyday life, we argue that a further exploration of parental understandings of child food allergy risk would benefit from an analysis of studies across different local contexts. In this article, we draw on a secondary qualitative cross-cultural analysis of interview data from several studies of parents in Sweden and Scotland through 2006–2010, which focused on parents’ understandings of the nature of food allergy and the children’s management of the allergy risk. We found some common themes in the different data sets. First, parents depicted food allergy as life-threatening, a ‘death risk’ lurking in the background, more or less constantly present in different everyday situations, amounting to an existential condition in parenting. Second, they talked about food allergy risk as a relational phenomenon, meaning that the risk emerged in the encounter between the young person’s individual competence to manage allergy risk and the understandings of allergy risk in others – thus depending on contexts and interaction between several actors. Finally, the analysis showed that unpredictability and risk in constant flux are the prominent aspects of living with food allergy. We also discussed the ways risk and trust are related, as well as how the involvement of others can be seen as both a risk and a safeguard.
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| 31. |
- Stork, D., et al.
(författare)
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Overview of transport, fast particle and heating and current drive physics using tritium in JET plasmas
- 2005
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Ingår i: Nuclear Fusion. - 0029-5515 .- 1741-4326. ; 45:10, s. S181-S194
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Tidskriftsartikel (refereegranskat)abstract
- Results are presented from the JET Trace Tritium Experimental (TTE) campaign using minority tritium (T) plasmas (n(T)/n(D) < 3%). Thermal tritium particle transport coefficients (D-T, nu(T)) are found to exceed neo-classical values in all regimes, except in ELMy H-modes at high densities and in the region of internal transport barriers (ITBs) in reversed shear plasmas. In ELMy H-mode dimensionless parameter scans, at q(95) 2.8 and triangularity delta = 0.2, the T particle transport scales in a gyro-Bohm manner in the inner plasma (r/a < 0.4), whilst the outer plasma particle transport scaling is more Bohm-like. Dimensionless parameter scans show contrasting behaviour for the trace particle confinement (increases with collisionality, nu* and beta) and bulk energy confinement (decreases with nu* and is independent of beta). In an extended ELMy H-mode data set, with rho*, nu*, and q varied but with neo-classical tearing modes (NTMs) either absent or limited to weak, benign core modes (4/3 or above), the multiparameter fit to the normalized diffusion coefficient in the outer plasma (0.65 < r/a < 0.8) gives D-T/B-phi similar to rho*(2.46) nu*(-0.23) beta(-1.01) q(2.03). In hybrid scenarios (q(min) similar to 1, low positive shear, no sawteeth), the T particle confinement is found to scale with increasing triangularity and plasma current. Comparing regimes (ELMy H-mode, ITB plasma and hybrid scenarios) in the outer plasma region, a correlation of high values of D-T with high values Of nu(T) is seen. The normalized diffusion coefficients for the hybrid and ITB scenarios do not fit the scaling derived for ELMy H-modes. The normalized tritium diffusion scales with normalized poloidal Larmor radius (rho(theta)* = q rho*) in a manner close to gyro-Bohm (similar to rho(sigma)*(3)), with an added inverse P dependence. The effects of ELMs, sawteeth and NTMs on the T particle transport are described. Fast-ion confinement in current-hole (CH) plasmas was tested in TTE by tritium neutral beam injection into JET CH plasmas. gamma-rays from the reactions of fusion alpha and beryllium impurities (Be-9(alpha, n gamma)C-12) characterized the fast fusion-alpha population evolution. The gamma-decay times are consistent with classical alpha plus parent fast triton slowing down times (tau(Ts) + tau(alpha s)) for high plasma currents (I-p > 2 MA) and monotonic q-profiles. In CH discharges the gamma-ray emission decay times are much lower than classical (tau(Ts) + tau(alpha s)), indicating alpha confinement degradation, due to the orbit losses and particle orbit drift predicted by a 3-D Fokker-Planck numerical code and modelled using TRANSP.
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| 32. |
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| 33. |
- Vinnes, Magnus K., et al.
(författare)
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The flow in the induction and entrance regions of lab-scale wind farms
- 2023
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Ingår i: Wind Energy. - : John Wiley & Sons. - 1095-4244 .- 1099-1824. ; 26:10, s. 1049-1065
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Tidskriftsartikel (refereegranskat)abstract
- With the increasing demand for wind energy, it is important to be able to understand and predict the available wind resources. To that end, the present wind tunnel study addresses the flow in the induction and entrance region of wind farms through particle image velocimetry, with focus on differences between actuator disks and two-bladed rotating wind turbine models. Both staggered and aligned farm layouts are examined for three different incoming wind directions. For each layout, 69 disks or turbines are used, and the field of view ranges from 12 rotor diameters upstream of the farms to 8 diameters downstream of the first row. The results show that the induction, or blockage effect, is higher for the disks, even though the thrust (or drag) coefficient is the same. In contrast, the wake is stronger downstream of the turbines. The orientation and layout of the farm do not have a major impact on the results. Modal decomposition of the flow shows that the flow structure similarity between the disk and turbines improves downstream of the second row of wake generating objects, indicating that the substitution of wind turbines by actuator disks is more appropriate for wind farms than for the investigation of single wakes.
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| 34. |
- Wu, Guorong, et al.
(författare)
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Excited state non-adiabatic dynamics of N-methylpyrrole : A time-resolved photoelectron spectroscopy and quantum dynamics study
- 2016
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 144:1
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Tidskriftsartikel (refereegranskat)abstract
- The dynamics of N-methylpyrrole following excitation at wavelengths in the range 241.5-217.0 nm were studied using a combination of time-resolved photoelectron spectroscopy (TRPES), ab initio quantum dynamics calculations using the multi-layer multi-configurational time-dependent Hartree method, as well as high-level photoionization cross section calculations. Excitation at 241.5 and 236.2 nm results in population of the A(2)(pi sigma*) state, in agreement with previous studies. Excitation at 217.0 nm prepares the previously neglected B-1(pi 3p(y)) Rydberg state, followed by prompt internal conversion to the A(2)(pi sigma*) state. In contrast with the photoinduced dynamics of pyrrole, the lifetime of the wavepacket in the A(2)(pi sigma*) state was found to vary with excitation wavelength, decreasing by one order of magnitude upon tuning from 241.5 nm to 236.2 nm and by more than three orders of magnitude when excited at 217.0 nm. The order of magnitude difference in lifetimes measured at the longer excitation wavelengths is attributed to vibrational excitation in the A(2)(pi sigma*) state, facilitating wavepacket motion around the potential barrier in the N-CH3 dissociation coordinate.
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| 35. |
- Wu, Guorong, et al.
(författare)
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Excited state non-adiabatic dynamics of pyrrole : A time-resolved photoelectron spectroscopy and quantum dynamics study
- 2015
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 142:7
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Tidskriftsartikel (refereegranskat)abstract
- The dynamics of pyrrole excited at wavelengths in the range 242-217 nm are studied using a combination of time-resolved photoelectron spectroscopy and wavepacket propagations performed using the multi-configurational time-dependent Hartree method. Excitation close to the origin of pyrrole's electronic spectrum, at 242 and 236 nm, is found to result in an ultrafast decay of the system from the ionization window on a single timescale of less than 20 fs. This behaviour is explained fully by assuming the system to be excited to the A(2)(pi sigma*) state, in accord with previous experimental and theoretical studies. Excitation at shorter wavelengths has previously been assumed to result predominantly in population of the bright A(1)(pi pi*) and B-2(pi pi*) states. We here present time-resolved photoelectron spectra at a pump wavelength of 217 nm alongside detailed quantum dynamics calculations that, together with a recent reinterpretation of pyrrole's electronic spectrum [S. P. Neville and G. A. Worth, J. Chem. Phys. 140, 034317 (2014)], suggest that population of the B-1(pi sigma*) state (hitherto assumed to be optically dark) may occur directly when pyrrole is excited at energies in the near UV part of its electronic spectrum. The B-1(pi sigma*) state is found to decay on a timescale of less than 20 fs by both N-H dissociation and internal conversion to the A(2)(pi sigma*) state.
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