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1.
Vet Pathol ; 61(3): 421-431, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38140946

RESUMO

The reemergence of the highly pathogenic avian influenza virus (HPAIV) subtype H5N1 in the United Kingdom in 2021-2022 has caused unprecedented epizootic events in wild birds and poultry. During the summer of 2022, there was a shift in virus transmission dynamics resulting in increased HPAIV infection in seabirds, and consequently, a profound impact on seabird populations. To understand the pathological impact of HPAIV in seabirds, we evaluated the virus antigen distribution and associated pathological changes in the tissues of great skua (Stercorarius skua, n = 8), long-tailed skua (Stercorarius longicaudus, n = 1), European herring gull (Larus argentatus, n = 5), and black-headed gull (Chroicocephalus ridibundus, n = 4), which succumbed to natural infection of HPAIV during the summer of 2022. Cases were collected from Shetland, including Scatness (mainland), No Ness (mainland), Clumlie (mainland), Hermaness (island), Fair Isle (island), Noss (island), and the West Midlands, South East, and South West of England. Grossly, gizzard ulceration was observed in one great skua and pancreatic necrosis was observed in 4 herring gulls, with intralesional viral antigen detected subsequently. Microscopical analysis revealed neuro-, pneumo-, lymphoid-, and cardiomyotropism of HPAIV H5N1, with the most common virus-associated pathological changes being pancreatic and splenic necrosis. Examination of the reproductive tract of the great skua revealed HPAIV-associated oophoritis and salpingitis, and virus replication within the oviductal epithelium. The emergence of HPAIV in seabirds Stercorariidae and Laridae, particularly during summer 2022, has challenged the dogma of HPAIV dynamics, posing a significant threat to wild bird life with potential implications for the reproductive performance of seabirds of conservation importance.


Assuntos
Charadriiformes , Virus da Influenza A Subtipo H5N1 , Influenza Aviária , Animais , Charadriiformes/virologia , Influenza Aviária/virologia , Influenza Aviária/patologia , Influenza Aviária/epidemiologia , Reino Unido/epidemiologia , Virus da Influenza A Subtipo H5N1/patogenicidade , Feminino
2.
Epidemiol Infect ; 151: e163, 2023 08 25.
Artigo em Inglês | MEDLINE | ID: mdl-37622315

RESUMO

Newcastle disease (ND) is a notifiable disease affecting chickens and other avian species caused by virulent strains of Avian paramyxovirus type 1 (APMV-1). While outbreaks of ND can have devastating consequences, avirulent strains of APMV-1 generally cause subclinical infections or mild disease. However, viruses can cause different levels of disease in different species and virulence can evolve following cross-species transmission events. This report describes the detection of three cases of avirulent APMV-1 infection in Great Britain (GB). Case 1 emerged from the 'testing to exclude' scheme in chickens in Shropshire while cases 2 and 3 were made directly from notifiable avian disease investigations in chicken broilers in Herefordshire and on premises in Wiltshire containing ducks and mixed species, respectively). Class II/genotype I.1.1 APMV-1 from case 1 shared 99.94% identity to the Queensland V4 strain of APMV-1. Class II/genotype II APMV-1 was detected from case 2 while the class II/genotype I.2 virus from case 3 aligned closely with strains isolated from Anseriformes. Exclusion of ND through rapid detection of avirulent APMV-1 is important where clinical signs caused by avirulent or virulent APMV-1s could be ambiguous. Understanding the diversity of APMV-1s circulating in GB is critical to understanding disease threat from these adaptable viruses.


Assuntos
Doenças das Aves , Doença de Newcastle , Animais , Galinhas , Reino Unido/epidemiologia , Vírus da Doença de Newcastle/genética , Doença de Newcastle/epidemiologia , Doença de Newcastle/diagnóstico , Filogenia
3.
J Phys Chem A ; 127(34): 7198-7204, 2023 Aug 31.
Artigo em Inglês | MEDLINE | ID: mdl-37594308

RESUMO

Excimeric systems (i.e., excited dimers) have well served as model compounds for the study of the delocalization of electronic energy over weakly interacting chromophores. However, there remain relatively few isolated systems in which such interactions can be studied experimentally at a level to afford detailed comparisons with theory. In this Article, we examine a series of covalently and noncovalently linked dimers of fluorene, as a model aromatic chromophore, where the formation of excimers requires a π-stacked, cofacial orientation at van der Waals contact. Building upon a series of seminal prior studies that examined vibronic quenching of the excitation interaction in van der Waals dimers, the key question that we sought to address here is whether a single quenching factor could reproduce experimental excitonic splittings across a series of covalently and noncovalently linked bichromophoric systems built from the same chromophore. In comparing experimentally measured excitonic splittings with calculated static splittings using time-dependent density functional methods, we find that all systems save one fall on a line with a slope of 0.080(8), reflecting a vibrational quenching of roughly 1 order of magnitude. The outlier, which shows a significantly reduced quenching factor, represents a cyclophane-linked system where the fluorene moieties are constrained in a cofacial arrangement. We argue that this system evidences the transition from the weak to intermediate coupling regime.

4.
Epidemiol Infect ; 151: e15, 2022 12 11.
Artigo em Inglês | MEDLINE | ID: mdl-36502812

RESUMO

Avian influenza (AI) is an important disease that has significant implications for animal and human health. High pathogenicity AI (HPAI) has emerged in consecutive seasons within the UK to cause the largest outbreaks recorded. Statutory measures to control outbreaks of AI virus (AIV) at poultry farms involve disposal of all birds on infected premises. Understanding of the timing of incursions into the UK could facilitate decisions on improved responses. During the autumnal migration and wintering period (autumn 2019- spring 2020), three active sampling approaches were trialled for wild bird species considered likely to be involved in captive AI outbreaks with retrospective laboratory testing undertaken to define the presence of AIV.Faecal sampling of birds (n = 594) caught during routine and responsive mist net sampling failed to detect AIV. Cloacal sampling of hunter-harvested waterfowl (n = 146) detected seven positive samples from three species with the earliest detection on the 17 October 2020. Statutory sampling first detected AIV in wild and captive birds on 3 November 2020. We conclude that hunter sourced sampling of waterfowl presents an opportunity to detect AI within the UK in advance of outbreaks on poultry farms and allow for early intervention measures to protect the national poultry flock.


Assuntos
Influenza Aviária , Animais , Humanos , Influenza Aviária/epidemiologia , Estudos Retrospectivos , Virulência , Conduta Expectante , Aves , Animais Selvagens , Aves Domésticas
5.
Epidemiol Infect ; 150: e51, 2022 02 10.
Artigo em Inglês | MEDLINE | ID: mdl-35139977

RESUMO

The 2016-17 European outbreak of H5N8 HPAIV (Clade 2.3.4.4b) affected a wider range of avian species than the previous H5N8 outbreak (2014-15), including an incursion of H5N8 HPAIV into gamebirds in England. Natural infection of captive-reared pheasants (Phasianus colchicus) led to variable disease presentation; clinical signs included ruffled feathers, reluctance to move, bright green faeces, and/or sudden mortality. Several birds exhibited neurological signs (nystagmus, torticollis, ataxia). Birds exhibiting even mild clinical signs maintained substantial levels of virus replication and shedding, with preferential shedding via the oropharyngeal route. Gross pathology was consistent with HPAIV, in gallinaceous species but diphtheroid plaques in oropharyngeal mucosa associated with necrotising stomatitis were novel but consistent findings. However, minimal or modest microscopic pathological lesions were detected despite the systemic dissemination of the virus. Serology results indicated differences in the timeframe of exposure for each case (n = 3). This supported epidemiological conclusions confirming that the movement of birds between sites and other standard husbandry practices with limited hygiene involved in pheasant rearing (including several fomite pathways) contributed to virus spread between premises.


Assuntos
Vírus da Influenza A Subtipo H5N8 , Vírus da Influenza A , Influenza Aviária , Animais , Aves , Surtos de Doenças/veterinária , Virulência
6.
Mol Breed ; 42(4): 17, 2022 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-37309457

RESUMO

To provide food security for a growing world population, it will be necessary to increase yields of staple crops such as wheat (Triticum aestivum L.). Yield is a complex, polygenic trait influenced by grain weight and number, which are negatively correlated with one another. Spikelet number is an important determinant of grain number, but allelic variants impacting its expression are often associated with heading date, constraining their use in wheat germplasm that must be adapted for specific environments. Identification and characterization of genetic variants affecting spikelet number will increase selection efficiency through their deployment in breeding programs. In this study, a quantitative trait locus (QTL) on chromosome arm 6BL for spikelet number was identified and validated using an association mapping panel, a recombinant inbred line population, and seven derived heterogeneous inbred families. The superior allele, QSn.csu-6Bb, was associated with an increase of 0.248 to 0.808 spikelets per spike across multiple environments that varied for mean spikelet number. Despite epistatic interactions between QSn.csu-6B and three other loci (WAPO-A1, VRN-D3, and PPD-B1), genotypes with a greater number of superior alleles at these loci consistently exhibit higher spikelet number. The frequency of superior alleles at these loci varies among winter wheat varieties adapted to different latitudes of the US Great Plains, revealing opportunities for breeders to select for increased spikelet number using simple molecular markers. This work lays the foundation for the positional cloning of the genetic variant underlying the QSn.csu-6B QTL to strengthen our understanding of spikelet number determination in wheat. Supplementary Information: The online version contains supplementary material available at 10.1007/s11032-022-01288-7.

7.
Emerg Infect Dis ; 27(11): 2856-2863, 2021 11.
Artigo em Inglês | MEDLINE | ID: mdl-34670647

RESUMO

We report a disease and mortality event involving swans, seals, and a fox at a wildlife rehabilitation center in the United Kingdom during late 2020. Five swans had onset of highly pathogenic avian influenza virus infection while in captivity. Subsequently, 5 seals and a fox died (or were euthanized) after onset of clinical disease. Avian-origin influenza A virus subtype H5N8 was retrospectively determined as the cause of disease. Infection in the seals manifested as seizures, and immunohistochemical and molecular testing on postmortem samples detected a neurologic distribution of viral products. The fox died overnight after sudden onset of inappetence, and postmortem tissues revealed neurologic and respiratory distribution of viral products. Live virus was isolated from the swans, seals, and the fox, and a single genetic change was detected as a potential adaptive mutation in the mammalian-derived viral sequences. No human influenza-like illness was reported in the weeks after the event.


Assuntos
Encefalite , Vírus da Influenza A Subtipo H5N8 , Influenza Aviária , Focas Verdadeiras , Animais , Centros de Reabilitação , Estudos Retrospectivos
8.
Environ Monit Assess ; 193(10): 680, 2021 Sep 30.
Artigo em Inglês | MEDLINE | ID: mdl-34591192

RESUMO

Fisheries monitoring can be improved by studying the influence of gear selectivity, sampling design, and habitat conditions. We used boat-electrofishing data to investigate how sample unit placement (shoreline and channel transects) and sampling conditions (low and high flow years) affect detection of fishes in a highly regulated Ontario (Canada) river system. Species detection histories associated with a spatially replicated sampling design was fit to a Bayesian hierarchical site occupancy model for 14 fishes. Habitat (transect location) had a significant effect on detection probabilities (p) for all species, with shoreline sampling more likely to detect species than channel. Sampling year had a significant effect on detectability of six species. The relative influence of habitat and sampling year varied among species. Detection probabilities based on combined shoreline and channel transect data across both years ranged from 0.09 to 0.48 and were positively correlated to species abundance. High detection probabilities and precise occupancy estimates were associated with sunfish and bass abundant in shoreline habitats. Small-bodied species closely associated with the riverbed or exhibiting schooling behavior tended to be poorly detected. Power to detect future changes in species distribution is expected to differ based on habitat sampled, with greater power associated with shoreline boat-electrofishing. Detecting small to moderate changes is not likely for most species. The addition of channel transects did not improve the effectiveness of shoreline sampling. Improvements to the current design could be realized by reallocating sampling effort from channel to shoreline and testing different gear in deep (> 3 m) habitats.


Assuntos
Monitoramento Ambiental , Navios , Animais , Teorema de Bayes , Ecossistema , Peixes , Ontário
9.
J Chem Phys ; 153(4): 044303, 2020 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-32752709

RESUMO

Recent studies of the weakly bound anisole⋯CH4 complex found a dual mode of binding, featuring both C/H⋯π and C/H⋯O noncovalent interactions. In this work, we examine the dissociation energies of related aniline⋯(CH4)n (n = 1, 2) van der Waals clusters, where both C/H⋯π and C/H⋯N interactions are possible. Using a combination of theory and experiments that include mass-selected two-color resonant two-photon ionization spectroscopy, two-color appearance potential (2CAP) measurements, and velocity-mapped ion imaging (VMI), we derive the dissociation energies of both complexes in the ground (S0), excited (S1), and cation radical (D0) states. As the amide group is non-planar in the ground state, the optimized ground state geometry of the aniline⋯CH4 1:1 complex shows two isomers, each with the methane positioned above the aniline ring. The observed redshift of the electronic origin from the aniline monomer is consistent with TDDFT calculations for the more stable isomer, where the methane sits on the same face as the amino hydrogens. The dissociation energies of the 1:1 complex, obtained from 2CAP measurements, are in good agreement with the calculated theoretical values from selected density functional theory methods. VMI data for the 1:1 complex gave a binding energy value overestimated by ∼179 cm-1 when compared to the 2CAP results, indicating that dissociative ionization selectively populates an excited vibrational level of the aniline cation radical. Given that the electron donating ability of aromatic substituents trends as -NH2 > -OCH3 > -CH3, it is noteworthy that the strength of methane binding also trends in this order, as found by experiment (dissociation energies in kJ/mol: 6.6 > 5.8 > 4.5) and predicted by theory (PBE0-D3/def2-QZVPPD, in kJ/mol: 6.9 > 6.0 > 5.0). For the 1:2 complex of aniline and methane, calculations predict that the more stable conformer is the one where the two methane molecules lie on opposite faces of the ring, consistent with the observed redshift of the electronic origin. Unlike the anisole-methane 1:2 complex, which shows an enhanced dissociation energy for the loss of one methane in comparison with the 1:1 complex, here, we find that the energy required to remove one methane from the ground state aniline-methane 1:2 complex is smaller than that of the 1:1 complex, consistent with theoretical expectations.

10.
J Phys Chem A ; 123(13): 2874-2880, 2019 Apr 04.
Artigo em Inglês | MEDLINE | ID: mdl-30860841

RESUMO

Noncovalent forces such as hydrogen bonding, halogen bonding, π-π stacking, and C-H/π and C-H/O interactions hold the key to such chemical processes as protein folding, molecular self-assembly, and drug-substrate interactions. Invaluable insight into the nature and strength of these forces continues to come from the study of isolated molecular clusters. In this work, we report on a study of the isolated anisole-methane complex, where both C-H/π and C-H/O interactions are possible, using a combination of theory and experiments that include mass-selected two-color resonant two-photon ionization spectroscopy, two-color appearance potential (2CAP) measurements, and velocity mapped ion imaging (VMI). Using 2CAP and VMI, we derive the binding energies of the complex in ground, excited, and cation radical states. The experimental values from the two methods are in excellent agreement, and they are compared with selected theoretical values calculated using density functional theory and ab initio methods. The optimized ground-state cluster geometry, which is consistent with the experimental observations, shows methane sitting above the ring, interacting with anisole via both C-H/π and C-H/O interactions, and this dual mode of interaction is reflected in a larger ground-state binding energy as compared with the prototypical benzene-methane system.


Assuntos
Anisóis/química , Carbono/química , Teoria da Densidade Funcional , Hidrogênio/química , Metano/química , Oxigênio/química , Ligação de Hidrogênio , Modelos Moleculares , Conformação Molecular
11.
Chemistry ; 24(66): 17439-17443, 2018 Nov 27.
Artigo em Inglês | MEDLINE | ID: mdl-30238528

RESUMO

Calixarenes have found widespread application as building blocks for the design and synthesis of functional materials in host-guest chemistry. The ongoing desire to develop a detailed understanding of the nature of NO bonding to multichromophoric π-stacked assemblies led us to develop an electron-rich methoxy derivative of calix[4]arene (3), which we show exists as a single conformer in solution at ambient temperature. Here, we examine the redox properties of this derivative, generate its cation radical (3+. ) using robust chemical oxidants, and determine the relative efficacy of its NO binding in comparison with model calixarenes. We find that 3/3+. is a remarkable receptor for NO+ /NO, with unprecedented binding efficacy. The availability of precise experimental structures of this calixarene derivative and its NO complex, obtained by X-ray crystallography, is critically important both for developing novel functional NO biosensors, and understanding the role of stacked aromatic donors in efficient NO binding, which may have relevance to biological NO transport.


Assuntos
Calixarenos/química , Óxido Nítrico/química , Fenóis/química , Calixarenos/metabolismo , Cátions , Cristalografia por Raios X , Técnicas Eletroquímicas , Espectroscopia de Ressonância de Spin Eletrônica , Transporte de Elétrons , Elétrons , Modelos Moleculares , Conformação Molecular , Óxido Nítrico/análise , Óxido Nítrico/metabolismo , Oxirredução , Fenóis/metabolismo , Termodinâmica
12.
Phys Chem Chem Phys ; 20(40): 25615-25622, 2018 Oct 17.
Artigo em Inglês | MEDLINE | ID: mdl-30283939

RESUMO

Ionization-induced structural and conformational reorganization in various π-stacked dimers and covalently linked bichromophores is relevant to many processes in biological systems and functional materials. In this work, we examine the role of structural, conformational, and solvent reorganization in a set of conformationally mobile bichromophoric donors, using a combination of gas-phase photoelectron spectroscopy, solution-phase electrochemistry, and density functional theory (DFT) calculations. Photoelectron spectral analysis yields both adiabatic and vertical ionization energies (AIE/VIE), which are compared with measured (adiabatic) solution-phase oxidation potentials (Eox). Importantly, we find a strong correlation of Eox with AIE, but not VIE, reflecting variations in the attendant structural/conformational reorganization upon ionization. A careful comparison of the experimental data with the DFT calculations allowed us to probe the extent of charge stabilization in the gas phase and solution and to parse the reorganizational energy into its various components. This study highlights the importance of a synergistic approach of experiment and theory to study ionization-induced structural and conformational reorganization.

13.
J Chem Phys ; 149(13): 134314, 2018 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-30292228

RESUMO

Studies of exciton and hole stabilization in multichromophoric systems underpin our understanding of electron transfer and transport in materials and biomolecules. The simplest model systems are dimeric, and recently we compared the gas-phase spectroscopy and dynamics of van der Waals dimers of fluorene, 9-methylfluorene (MF), and 9,9'-dimethylfluorene (F1) to assess how sterically controlled facial encumbrance modulates the dynamics of excimer formation and charge resonance stabilization (CRS). Dimers of fluorene and MF show only excimer emission upon electronic excitation, and significant CRS as evidenced in a reduced ionization potential for the dimer relative the monomer. By contrast, the dimer of F1 shows no excimeric emission, rather structured emission from the locally excited state of a tilted (non π-stacked) dimer, evidencing the importance of C-H/π interactions and increased steric constraints that restrict a cofacial approach. In this work, we report our full results on van der Waals clusters of F1, using a combination of theory and experiments that include laser-induced fluorescence, mass-selected two-color resonant two-photon ionization spectroscopy, and two-color appearance potential measurements. We use the latter to derive the binding energies of the F1 dimer in ground, excited, and cation radical states. Our results are compared with van der Waals and covalently linked clusters of fluorene to assess both the relative strength of π-stacking and C-H/π interactions in polyaromatic assemblies and the role of π-stacking in excimer formation and CRS.

14.
Cryobiology ; 82: 8-14, 2018 06.
Artigo em Inglês | MEDLINE | ID: mdl-29723505

RESUMO

Conserving genetic diversity is a major priority of the National Laboratory for Genetic Resources Preservation (NLGRP), operated by the U.S. Department of Agriculture, Agricultural Research Service. There are two long-term preservation methods employed in the NLGRP: storage in a -18 °C freezer (conventional storage) and storage in liquid nitrogen vapor phase at -135 to -180 °C (cryopreservation). To test the phenotypic and epigenetic effects of long-term cryopreservation of orthodox seeds, we evaluated 40 cereal rye accessions (20 spring habit and 20 winter habit) stored for 25 years under both conventional storage and cryogenic conditions. In laboratory evaluations of winter habit rye, seeds from cryopreserved samples had significantly higher normal germination percentage (P < 0.05) and lower abnormal germination percentage (P < 0.05) than those stored under conventional conditions. Cryopreserved spring habit rye also had higher normal germination percentage (P < 0.01) than conventionally stored samples. In addition, winter rye seedlings from cryopreserved seeds had longer roots and smaller root diameter (P < 0.05) than seedlings from conventionally stored seeds. In field evaluations conducted in Fort Collins, Colorado in 2014-15, spikes of plants grown from conventionally stored seeds of the winter accessions were slightly longer than those from cryopreserved seeds (P = 0.045). To detect DNA methylation changes, a methylation-sensitive amplified fragment length polymorphism (metAFLP) technique was applied to two accessions. After false discovery rate adjustment, no differences in methylation were detected between storage treatments on an individual locus basis. Our study indicated that cryopreservation slowed seed deterioration as evidenced by higher germination rates compared to conventional storage, had only minimal effects on other phenotypic traits, and had no significant effects on DNA methylation status.


Assuntos
Criopreservação/métodos , Metilação de DNA/genética , Raízes de Plantas/crescimento & desenvolvimento , Secale/crescimento & desenvolvimento , Secale/genética , Plântula/crescimento & desenvolvimento , Sementes/crescimento & desenvolvimento , Análise do Polimorfismo de Comprimento de Fragmentos Amplificados , Germinação , Nitrogênio/farmacologia , Fenótipo , Plantas
15.
MAGMA ; 31(1): 183-190, 2018 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-28653214

RESUMO

OBJECTIVE: The purpose of this work is to evaluate the repeatability of a compressed sensing (CS) accelerated multi-contrast carotid protocol at 3 T. MATERIALS AND METHODS: Twelve volunteers and eight patients with carotid disease were scanned on a 3 T MRI scanner using a CS accelerated 3-D black-blood multi-contrast protocol which comprises T 1w, T 2w and PDw without CS, and with a CS factor of 1.5 and 2.0. The volunteers were scanned twice, the lumen/wall area and wall thickness were measured for each scan. Eight patients were scanned once, the inter/intra-observer reproducibility of the measurements was calculated. RESULTS: In the repeated volunteer scans, the interclass correlation coefficient (ICC) for the wall area measurement using a CS factor of 1.5 in PDw, T 1w and T 2w were 0.95, 0.81, and 0.97, respectively. The ICC for lumen area measurement using a CS factor of 1.5 in PDw, T 1w and T 2w were 0.96, 0.92, and 0.96, respectively. In patients, the ICC for inter/intra-observer measurements of lumen/wall area, and wall thickness were all above 0.81 in all sequences. CONCLUSION: The results show a CS accelerated 3-D black-blood multi-contrast protocol is a robust and reproducible method for carotid imaging. Future protocol design could use CS to reduce the scanning time.


Assuntos
Técnicas de Imagem Cardíaca/métodos , Artérias Carótidas/diagnóstico por imagem , Angiografia por Ressonância Magnética/métodos , Adulto , Idoso , Idoso de 80 Anos ou mais , Técnicas de Imagem Cardíaca/estatística & dados numéricos , Estenose das Carótidas/diagnóstico por imagem , Estudos de Casos e Controles , Meios de Contraste , Compressão de Dados , Feminino , Voluntários Saudáveis , Humanos , Interpretação de Imagem Assistida por Computador/métodos , Imageamento Tridimensional/métodos , Imageamento Tridimensional/estatística & dados numéricos , Angiografia por Ressonância Magnética/estatística & dados numéricos , Imageamento por Ressonância Magnética/métodos , Imageamento por Ressonância Magnética/estatística & dados numéricos , Masculino , Pessoa de Meia-Idade , Reprodutibilidade dos Testes , Adulto Jovem
16.
Angew Chem Int Ed Engl ; 57(27): 8189-8193, 2018 07 02.
Artigo em Inglês | MEDLINE | ID: mdl-29733488

RESUMO

Exciton and charge delocalization across π-stacked assemblies is of importance in biological systems and functional polymeric materials. To examine the requirements for exciton and hole stabilization, cofacial bifluorene (F2) torsionomers were designed, synthesized, and characterized: unhindered (model) Me F2, sterically hindered tBu F2, and cyclophane-like C F2, where fluorenes are locked in a perfect sandwich orientation via two methylene linkers. This set of bichromophores with varied torsional rigidity and orbital overlap shows that exciton stabilization requires a perfect sandwich-like arrangement, as seen by strong excimeric-like emission only in C F2 and Me F2. In contrast, hole delocalization is less geometrically restrictive and occurs even in sterically hindered tBu F2, as judged by 160 mV hole stabilization and a near-IR band in the spectrum of its cation radical. These findings underscore the diverse requirements for charge and energy delocalization across π-stacked assemblies.


Assuntos
Fluorenos/química , Técnicas Eletroquímicas , Espectrometria de Fluorescência , Termodinâmica
17.
Hum Factors ; 59(7): 1108-1127, 2017 11.
Artigo em Inglês | MEDLINE | ID: mdl-28574734

RESUMO

Objective Four sets of eight audible alarms matching the functions specified in IEC 60601-1-8 were designed using known principles from auditory cognition with the intention that they would be more recognizable and localizable than those currently specified in the standard. Background The audible alarms associated with IEC 60601-1-8, a global medical device standard, are known to be difficult to learn and retain, and there have been many calls to update them. There are known principles of design and cognition that might form the basis of more readily recognizable alarms. There is also scope for improvement in the localizability of the existing alarms. Method Four alternative sets of alarms matched to the functions specified in IEC 60601-1-8 were tested for recognizability and localizability and compared with the alarms currently specified in the standard. Results With a single exception, all prototype sets of alarms outperformed the current IEC set on both recognizability and localizability. Within the prototype sets, auditory icons were the most easily recognized, but the other sets, using word rhythms and simple acoustic metaphors, were also more easily recognized than the current alarms. With the exception of one set, all prototype sets were also easier to localize. Conclusion Known auditory cognition and perception principles were successfully applied to an existing audible alarm problem. Application This work constitutes the first (benchmarking) phase of replacing the alarms currently specified in the standard. The design principles used for each set demonstrate the relative ease with which different alarm types can be recognized and localized.


Assuntos
Percepção Auditiva/fisiologia , Alarmes Clínicos/normas , Equipamentos e Provisões Elétricas/normas , Desenho de Equipamento/normas , Adulto , Humanos
18.
Radiology ; 279(2): 368-77, 2016 May.
Artigo em Inglês | MEDLINE | ID: mdl-26579563

RESUMO

PURPOSE: To investigate the effects of radiofrequency transmit field (B1(+)) correction on (a) the measured T1 relaxation times of normal breast tissue and malignant lesions and (b) the pharmacokinetically derived parameters of malignant breast lesions at 3 T. MATERIALS AND METHODS: Ethics approval and informed consent were obtained. Between May 2013 and January 2014, 30 women (median age, 58 years; range, 32-83 years) with invasive ductal carcinoma of at least 10 mm were recruited to undergo dynamic contrast material-enhanced magnetic resonance (MR) imaging before surgery. B1(+) and T1 mapping sequences were performed to determine the effect of B1(+) correction on the native tissue relaxation time (T10) of fat, parenchyma, and malignant lesions in both breasts. Pharmacokinetic parameters were calculated before and after correction for B1(+) variations. Results were correlated with histologic grade by using the Kruskal-Wallis test. RESULTS: Measurements showed a mean 37% flip angle difference between the right and left breast, which resulted in a 61% T10 difference in fat and a 41.5% difference in parenchyma between the two breasts. The T1 of lesions in the right breast increased by 58%, whereas that of lesions in the left breast decreased by 30% after B1(+) correction. The whole-tumor transendothelial permeability across the vascular compartment(K(trans)) of lesions in the right breast decreased by 41%, and that of lesions in the left breast increased by 46% after correction. A systematic increase in K(trans) was observed, with significant differences found across the histologic grades (P < .001). The effect size of B1(+) correction on K(trans) calculation was large for lesions in the right breast and moderate for lesions in the left breast (Cohen effect size, d = 0.86 and d = 0.59, respectively). CONCLUSION: B1(+) correction demonstrates a substantial effect on the results of quantitative dynamic contrast-enhanced analysis of breast tissue at 3 T, which propagates into the pharmacokinetic analysis of tumors that is dependent on whether the tumor is located in the right or left breast.


Assuntos
Neoplasias da Mama/patologia , Carcinoma Ductal de Mama/patologia , Imageamento por Ressonância Magnética/métodos , Adulto , Idoso , Idoso de 80 Anos ou mais , Biópsia , Neoplasias da Mama/cirurgia , Carcinoma Ductal de Mama/cirurgia , Meios de Contraste/farmacocinética , Feminino , Humanos , Interpretação de Imagem Assistida por Computador , Pessoa de Meia-Idade , Estadiamento de Neoplasias , Estudos Prospectivos , Razão Sinal-Ruído
19.
J Virol ; 89(19): 9920-31, 2015 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-26202246

RESUMO

UNLABELLED: The emergence in humans of the A(H1N1)pdm09 influenza virus, a complex reassortant virus of swine origin, highlighted the importance of worldwide influenza virus surveillance in swine. To date, large-scale surveillance studies have been reported for southern China and North America, but such data have not yet been described for Europe. We report the first large-scale genomic characterization of 290 swine influenza viruses collected from 14 European countries between 2009 and 2013. A total of 23 distinct genotypes were identified, with the 7 most common comprising 82% of the incidence. Contrasting epidemiological dynamics were observed for two of these genotypes, H1huN2 and H3N2, with the former showing multiple long-lived geographically isolated lineages, while the latter had short-lived geographically diffuse lineages. At least 32 human-swine transmission events have resulted in A(H1N1)pdm09 becoming established at a mean frequency of 8% across European countries. Notably, swine in the United Kingdom have largely had a replacement of the endemic Eurasian avian virus-like ("avian-like") genotypes with A(H1N1)pdm09-derived genotypes. The high number of reassortant genotypes observed in European swine, combined with the identification of a genotype similar to the A(H3N2)v genotype in North America, underlines the importance of continued swine surveillance in Europe for the purposes of maintaining public health. This report further reveals that the emergences and drivers of virus evolution in swine differ at the global level. IMPORTANCE: The influenza A(H1N1)pdm09 virus contains a reassortant genome with segments derived from separate virus lineages that evolved in different regions of the world. In particular, its neuraminidase and matrix segments were derived from the Eurasian avian virus-like ("avian-like") lineage that emerged in European swine in the 1970s. However, while large-scale genomic characterization of swine has been reported for southern China and North America, no equivalent study has yet been reported for Europe. Surveillance of swine herds across Europe between 2009 and 2013 revealed that the A(H1N1)pdm09 virus is established in European swine, increasing the number of circulating lineages in the region and increasing the possibility of the emergence of a genotype with human pandemic potential. It also has implications for veterinary health, making prevention through vaccination more challenging. The identification of a genotype similar to the A(H3N2)v genotype, causing zoonoses at North American agricultural fairs, underlines the importance of continued genomic characterization in European swine.


Assuntos
Vírus da Influenza A/genética , Infecções por Orthomyxoviridae/veterinária , Sus scrofa/virologia , Doenças dos Suínos/epidemiologia , Doenças dos Suínos/virologia , Animais , Monitoramento Epidemiológico/veterinária , Europa (Continente)/epidemiologia , Evolução Molecular , Genótipo , Humanos , Vírus da Influenza A Subtipo H1N1/genética , Vírus da Influenza A Subtipo H1N1/isolamento & purificação , Vírus da Influenza A Subtipo H1N2/genética , Vírus da Influenza A Subtipo H1N2/isolamento & purificação , Vírus da Influenza A Subtipo H3N2/genética , Vírus da Influenza A Subtipo H3N2/isolamento & purificação , Vírus da Influenza A/isolamento & purificação , Influenza Humana/epidemiologia , Influenza Humana/virologia , Epidemiologia Molecular , Infecções por Orthomyxoviridae/epidemiologia , Infecções por Orthomyxoviridae/virologia , Filogenia , Vírus Reordenados/genética , Suínos
20.
J Org Chem ; 81(4): 1627-34, 2016 Feb 19.
Artigo em Inglês | MEDLINE | ID: mdl-26783949

RESUMO

Multiple molecular wires braided together in a single assembly, termed as molecular cable, are promising next-generation materials for effective long-range charge transport. As an example of the platform for constructing molecular cables, 1,3,5-trifluorenylcyclohexane (TFC) and its difluorenyl analogues (DFCs) were systematically investigated both experimentally (X-ray crystallography) and theoretically (DFT calculations). Although the syntheses of DFCs were successfully achieved, the synthesis of TFC, which involved a similar intramolecular Friedel-Crafts cyclization as the last step, was unsuccessful. An exhaustive study of the conformational landscape of cyclohexane ring of TFC and DFCs revealed that TFC is a moderately strained molecule (∼17 kcal/mol), and computational studies of the reaction profile show that this steric strain, present in the transition state, is responsible for the unusually high (∼5 years) reaction half-life. A successful synthesis of TFC will require that the steric strain is introduced in multiple steps, and such alternative strategies are being currently explored.


Assuntos
Fluorbenzenos/síntese química , Cristalografia por Raios X , Fluorbenzenos/química , Modelos Moleculares , Conformação Molecular
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