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Observing the crucial first few femtoseconds of photochemical reactions requires tools typically not available in the femtochemistry toolkit. Such dynamics are now within reach with the instruments provided by attosecond science. Here, we apply experimental and theoretical methods to assess the ultrafast nonadiabatic vibronic processes in a prototypical complex system-the excited benzene cation. We use few-femtosecond duration extreme ultraviolet and visible/near-infrared laser pulses to prepare and probe excited cationic states and observe two relaxation timescales of 11 ± 3 fs and 110 ± 20 fs. These are interpreted in terms of population transfer via two sequential conical intersections. The experimental results are quantitatively compared with state-of-the-art multi-configuration time-dependent Hartree calculations showing convincing agreement in the timescales. By characterising one of the fastest internal conversion processes studied to date, we enter an extreme regime of ultrafast molecular dynamics, paving the way to tracking and controlling purely electronic dynamics in complex molecules.
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BACKGROUND: Over half of men who receive treatment for prostate suffer from a range of sexual problems that affect negatively their sexual health, sexual intimacy with their partners and their quality of life. In clinical practice, however, care for the sexual side effects of treatment is often suboptimal or unavailable. The goal of the current study is to test a web-based intervention to support the recovery of sexual intimacy of prostate cancer survivors and their partners after treatment. METHODS: The study team developed an interactive, web-based intervention, tailored to type of treatment received, relationship status (partnered/non-partnered) and sexual orientation. It consists of 10 modules, six follow the trajectory of the illness and four are theme based. They address sexual side effects, rehabilitation, psychological impacts and coaching for self-efficacy. Each includes a video to engage participants, psychoeducation and activities completed by participants on the web. Tailored strategies for identified concerns are sent by email after each module. Six of these modules will be tested in a randomized controlled trial and compared to usual care. Men with localized prostate cancer with partners will be recruited from five academic medical centers. These couples (N = 140) will be assessed prior to treatment, then 3 months and 6 months after treatment. The primary outcome will be the survivors' and partners' Global Satisfaction with Sex Life, assessed by a Patient Reported Outcome Measure Information Systems (PROMIS) measure. Secondary outcomes will include interest in sex, sexual activity, use of sexual aids, dyadic coping, knowledge about sexual recovery, grief about the loss of sexual function, and quality of life. The impact of the intervention on the couple will be assessed using the Actor-Partner Interaction Model, a mixed-effects linear regression model able to estimate both the association of partner characteristics with partner and patient outcomes and the association of patient characteristics with both outcomes. DISCUSSION: The web-based tool represents a novel approach to addressing the sexual health needs of prostate cancer survivors and their partners that-if found efficacious-will improve access to much needed specialty care in prostate cancer survivorship. TRIAL REGISTRATION: Clinicaltrials.gov registration # NCT02702453 , registered on March 3, 2016.
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Neoplasias da Próstata/epidemiologia , Disfunções Sexuais Fisiológicas/epidemiologia , Disfunções Sexuais Psicogênicas/epidemiologia , Estresse Psicológico , Adolescente , Adulto , Feminino , Humanos , Internet , Masculino , Pessoa de Meia-Idade , Neoplasias da Próstata/complicações , Neoplasias da Próstata/fisiopatologia , Neoplasias da Próstata/psicologia , Qualidade de Vida , Comportamento Sexual/fisiologia , Comportamento Sexual/psicologia , Disfunções Sexuais Fisiológicas/etiologia , Disfunções Sexuais Fisiológicas/fisiopatologia , Disfunções Sexuais Psicogênicas/etiologia , Disfunções Sexuais Psicogênicas/fisiopatologia , Parceiros Sexuais , Cônjuges/psicologia , Adulto JovemRESUMO
Unraveling ultrafast dynamical processes in highly excited molecular species has an impact on our understanding of chemical processes such as combustion or the chemical composition of molecular clouds in the universe. In this article we use short (<7 fs) XUV pulses to produce excited cationic states of benzene molecules and probe their dynamics using few-cycle VIS/NIR laser pulses. The excited states produced by the XUV pulses lie in an especially complex spectral region where multi-electronic effects play a dominant role. We show that very fast τ ≈ 20 fs nonadiabatic processes dominate the relaxation of these states, in agreement with the timescale expected for most excited cationic states in benzene. In the CH3+ fragmentation channel of the doubly ionized benzene cation we identify pathways that involve structural rearrangement and proton migration to a specific carbon atom. Further, we observe non-trivial transient behavior in this fragment channel, which can be interpreted either in terms of propagation of the nuclear wavepacket in the initially excited electronic state of the cation or as a two-step electronic relaxation via an intermediate state.
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We quantified the amount of plastic found in food loads delivered to nestlings in Cassin's Auklet (Ptychoramphus aleuticus), a small, zooplanktivorous seabird, on Triangle Island, British Columbia, in 1996-2016. The density of plastic in surrounding waters is moderately high, yet few food loads contained any plastic (3 of 850), and none more than two pieces. That result accords well with previous observations on the other four North Pacific auklets (Aethia spp.), leading us to conclude that true auklets rarely transfer plastic to nestlings. However, many hatch-year Cassin's Auklets found dead in coastal British Columbia, Washington and Oregon during the mass mortality event of fall and winter 2014-15 had plastic in their ventriculi. We suggest that these plastic particles would have been obtained at sea after fledging, perhaps while the birds transited south through a region of high plastic density off the west coast of Vancouver Island, Washington and Oregon.
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Plásticos/análise , Poluentes da Água/análise , Zooplâncton/química , Animais , Animais Recém-Nascidos , Aves , Colúmbia Britânica , Comportamento Alimentar , Incidência , Oregon , WashingtonRESUMO
Time-resolved extreme ultraviolet (XUV) transient absorption spectroscopy of iodomethane and iodobenzene photodissociation at the iodine pre-N4,5 edge is presented, using femtosecond UV pump pulses and XUV probe pulses from high harmonic generation. For both molecules the molecular core-to-valence absorption lines fade immediately, within the pump-probe time-resolution. Absorption lines converging to the atomic iodine product emerge promptly in CH3I but are time-delayed in C6H5I. We attribute this delay to the initial π â σ(*) excitation in iodobenzene, which is distant from the iodine reporter atom. We measure a continuous shift in energy of the emerging atomic absorption lines in CH3I, attributed to relaxation of the excited valence shell. An independent particle model is used to rationalize the observed experimental findings.
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Despite the availability of selenium (Se)-enriched trace mineral supplements, we have observed low Se status in cattle and sheep offered traditional inorganic Se supplements. Reasons for this may include inadequate intake or low bioavailability of inorganic Se sources. The objective of this study was to determine whether rumen microorganisms (RMO) alter the bioavailability of Se sources commonly used in Se supplements. Rumen microorganisms were isolated from ewes (n = 4) and incubated ex vivo with no Se (control), with inorganic Na selenite or Na selenate, or with organic selenomethionine (SeMet). Total Se incorporated into RMO and the amount of elemental Se formed were determined under equivalent conditions. Incorporation of Se from Na selenite, Na selenate, or SeMet into RMO was measured as fold change compared with control (no added Se). Incorporation of Se into microbial mass was greater for SeMet (13.2-fold greater than no-Se control) compared with inorganic Se supplements (P = 0.02); no differences were observed between inorganic Na selenate (3.3-fold greater than no-Se control) and Na selenite (3.5-fold greater than no-Se control; P = 0.97). Formation of non-bioavailable, elemental Se was less for RMO incubated with SeMet compared with inorganic Se sources (P = 0.01); no differences were observed between Na selenate and Na selenite (P = 0.09). The clinical importance of these results is that the oral bioavailability of organic SeMet should be greater compared with inorganic Se sources because of greater RMO incorporation of Se and decreased formation of elemental Se by RMO.
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Rúmen/metabolismo , Rúmen/microbiologia , Selênio/farmacocinética , Ovinos/metabolismo , Ovinos/microbiologia , Administração Oral , Animais , Disponibilidade Biológica , Suplementos Nutricionais , Feminino , Selênio/administração & dosagem , Selênio/metabolismoRESUMO
Highly excited molecular species are at play in the chemistry of interstellar media and are involved in the creation of radiation damage in a biological tissue. Recently developed ultrashort extreme ultraviolet light sources offer the high excitation energies and ultrafast time-resolution required for probing the dynamics of highly excited molecular states on femtosecond (fs) (1 fs=10(-15) s) and even attosecond (as) (1 as=10(-18) s) timescales. Here we show that polycyclic aromatic hydrocarbons (PAHs) undergo ultrafast relaxation on a few tens of femtoseconds timescales, involving an interplay between the electronic and vibrational degrees of freedom. Our work reveals a general property of excited radical PAHs that can help to elucidate the assignment of diffuse interstellar absorption bands in astrochemistry, and provides a benchmark for the manner in which coupled electronic and nuclear dynamics determines reaction pathways in large molecules following extreme ultraviolet excitation.
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Hole migration is a fascinating process driven by electron correlation, in which purely electronic dynamics occur on a very short time scale in complex ionized molecules, prior to the onset of nuclear motion. However, it is expected that due to coupling to the nuclear dynamics, these oscillations will be rapidly damped and smeared out, which makes experimental observation of the hole migration process rather difficult. In this Letter, we demonstrate that the instantaneous ionization of benzene molecules initiates an ultrafast hole migration characterized by a periodic breathing of the hole density between the carbon ring and surrounding hydrogen atoms on a subfemtosecond time scale. We show that these oscillations survive the dephasing introduced by the nuclear motion for a long enough time to allow their observation. We argue that this offers an ideal benchmark for studying the influence of hole migration on molecular reactivity.
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Variation in the diet of the Pacific sand lance Ammodytes hexapterus was examined in three years (2009-2011) at four sites in British Columbia, Canada. There were 12 major taxa of prey in diets, eight of which were Crustacea, with copepods being by far the dominant taxon in all 12 site-years. Of the 22 copepod taxa recorded, only Calanus marshallae and Pseudocalanus spp. occurred in all collections, and these two calanoid species dominated diets in terms of frequency of occurrence and total numbers of prey (Pseudocalanus spp. in most collections), and total prey biomass (C. marshallae in all collections). Based on an index of relative importance, C. marshallae was the primary prey at the two southerly sampling sites (Pine and Triangle Islands) and Pseudocalanus spp. at the two northerly sites (Lucy Island and S'Gang Gwaay). Based on an index of dietary overlap, the species composition of the copepod component of A. hexapterus diets overlapped very strongly at the northerly and the southerly pairs of sites in both a cold-water La Niña year (2009) and a warm-water El Niño year (2010), but overall there was more homogeneity amongst all four sites in the La Niña year.
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Dieta , Perciformes/fisiologia , Animais , Colúmbia Britânica , Charadriiformes , Crustáceos , El Niño Oscilação Sul , Cadeia Alimentar , Conteúdo Gastrointestinal , Geografia , Oceano Pacífico , Análise Espaço-TemporalRESUMO
From October 4 to November 2, 2001, the first 10 confirmed cases of inhalational anthrax caused by intentional release of Bacillus anthracis were identified in the United States. Epidemiologic investigation indicated that the outbreak, in the District of Columbia, Florida, New Jersey, and New York, resulted from intentional delivery of B. anthracis spores through mailed letters or packages. We describe the clinical presentation and course of these cases of bioterrorism-related inhalational anthrax. The median age of patients was 56 years (range 43 to 73 years), 70% were male, and except for one, all were known or believed to have processed, handled, or received letters containing B. anthracis spores. The median incubation period from the time of exposure to onset of symptoms, when known (n=6), was 4 days (range 4 to 6 days). Symptoms at initial presentation included fever or chills (n=10), sweats (n=7), fatigue or malaise (n=10), minimal or nonproductive cough (n=9), dyspnea (n=8), and nausea or vomiting (n=9). The median white blood cell count was 9.8 X 10(3)/mm(3) (range 7.5 to 13.3), often with increased neutrophils and band forms. Nine patients had elevated serum transaminase levels, and six were hypoxic. All 10 patients had abnormal chest X-rays; abnormalities included infiltrates (n=7), pleural effusion (n=8), and mediastinal widening (seven patients). Computed tomography of the chest was performed on eight patients, and mediastinal lymphadenopathy was present in seven. With multidrug antibiotic regimens and supportive care, survival of patients (60%) was markedly higher (<15%) than previously reported.
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Antraz/fisiopatologia , Bioterrorismo , Exposição por Inalação/efeitos adversos , Adulto , Idoso , Antraz/epidemiologia , Antraz/transmissão , Bacillus anthracis/fisiologia , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Estados Unidos/epidemiologiaRESUMO
PURPOSE/OBJECTIVES: To describe how different treatments for prostate cancer affect health-related quality of life (QOL), health status, and masculinity. DESIGN: Longitudinal survey design with descriptive, correlational, and comparative elements. SETTING: A tertiary medical center and associated clinics in a suburban community in the Southwestern United States. SAMPLE: 185 men with localized prostate cancer were enrolled from five treatment groups: watchful waiting (n = 30), surgery (n = 59), conventional radiation (n = 25), proton-beam radiation (n = 24), and a combination of conventional radiation and proton-beam radiation or mixed-beam radiation (n = 47). At six months, 163 remained on the study; at 12 months, 154 remained: and at 18 months, 153 remained. The average age was 68 years, and 82% of the men were white. METHODS: Men were enrolled at treatment and given a questionnaire with a self-addressed, stamped envelope for return. Questionnaires were mailed again at 6, 12, and 18 months. MAIN RESEARCH VARIABLES: Health-related QOL health status, prostate treatment-specific symptoms, and sex-role identity. FINDINGS: No overall difference in health-related QOL or health status was found, but post-hoc analysis revealed specific differences. The differences existed in sexual functioning and gastrointestinal treatment-specific symptoms. No relationship existed between masculinity and health-related QOL. CONCLUSIONS: Health-related QOL and health status are similar regardless of type of treatment. Radiation tends to produce more gastrointestinal symptoms, and surgery tends to produce more sexual functioning symptoms. Watchful waiting is associated with poorer general health. IMPLICATIONS FOR NURSING PRACTICE: Nurses can provide specific treatment-related information to men who are faced with making treatment decisions for prostate cancer and, in consultation with the healthcare team, can select a treatment best sulted to them.
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Identidade de Gênero , Neoplasias da Próstata/enfermagem , Neoplasias da Próstata/psicologia , Qualidade de Vida , Idoso , Humanos , Estudos Longitudinais , Masculino , Enfermagem Oncológica , Neoplasias da Próstata/radioterapia , Neoplasias da Próstata/cirurgia , Inquéritos e Questionários , Resultado do TratamentoRESUMO
A pilot study examined the specific cognitive content of female adolescents with anorexia nervosa. The relationship between daughter and mother concerns, and concerns in mothers, also were investigated. All participants completed a measure of assumptions and negative self-beliefs related to eating disorders. Adolescents with anorexia nervosa scored more highly on all subscales of the measure than nonclinical adolescent controls. There were significant daughter-mother relationships on two subscales in the clinical, but not the nonclinical, group. However, the two groups of mothers did not differ on any subscale. Possible explanations for the findings, and implications for treatment and research, are briefly considered.
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Many studies have examined the experiences of patients who have had coronary artery bypass graft (CABG) surgery. Research has suggested a relationship between patients' feelings of powerlessness and their recovery rate. This study examined recovery indicators and the degree of powerlessness CABG patients experienced, and identified ways nurses can encourage patients to participate in their recovery and feel back in control.
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Atitude Frente a Saúde , Ponte de Artéria Coronária/psicologia , Poder Psicológico , Adulto , Idoso , Idoso de 80 Anos ou mais , Ponte de Artéria Coronária/reabilitação , Exercício Físico/fisiologia , Feminino , Humanos , Tempo de Internação/estatística & dados numéricos , Masculino , Pessoa de Meia-Idade , Dor Pós-Operatória/psicologia , Estudos Retrospectivos , Fatores de RiscoRESUMO
OBJECTIVE: Alcohol-involved crashes cost society more than $100 billion a year. Sobriety checkpoints are effective in apprehending drunk drivers. This article compares the costs and the estimated monetary benefits from a hypothetical community sobriety checkpoint program. METHOD: The analysis is constructed around a hypothetical community with 100,000 licensed drivers. A literature review suggests that a generously funded intensive checkpoint program (156 checkpoints per year) can be expected to reduce alcohol-attributable crashes by about 15%. The benefits (cost savings) of the checkpoint program are calculated using 1993 alcohol-involved crash incidence from the National Highway Traffic Safety Administration. Costs per alcohol-involved crash and the percentage of alcohol-involved crashes attributable to alcohol are updated from published studies. RESULTS: Estimated annual savings to the hypothetical community total $7.9 million. This includes $3.1 million for averted fatalities, $4.5 million for averted non-fatal injuries, and $0.3 million for averted property damage. Every $1 spent on a sobriety checkpoint program can be expected to save the community more than $6, including $1.30 of insurer costs. CONCLUSIONS: An intensive sobriety checkpoint program can save a community more in automobile crash costs than the program costs.
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Acidentes de Trânsito/prevenção & controle , Intoxicação Alcoólica/prevenção & controle , Controle Social Formal , Temperança/economia , Acidentes de Trânsito/economia , Intoxicação Alcoólica/economia , Análise Custo-Benefício , Humanos , Seguro de Acidentes/economia , Estados UnidosRESUMO
The personal and societal losses caused by motor-vehicle crashes are significant. This paper provides tools that describe these losses for 30 different crash geometries. Persons involved with the development and implementation of crash countermeasures can use these tools to prioritize their countermeasure approach. Multiple vehicle crashes currently account for much larger direct costs but only slightly more years lost than single vehicle crashes. Direct expenditures on multiple vehicle crashes exceed $41 billion per year; they claim 974,000 years of life and functioning. Direct expenditures on single vehicle crashes exceed $18 billion per year; they claim 937,000 years of life and functioning.
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Acidentes de Trânsito/economia , Custos e Análise de Custo , Humanos , Veículos Automotores , Estados UnidosRESUMO
Non-insulin-dependent diabetes mellitus (NIDDM) has been associated with stressful events such as immigration. The purpose of this paper is to report a pilot study that tested translated and back-translated instruments to ascertain factors related to diabetes management in a group of Chinese immigrants with diabetes. The descriptive, cross-sectional design included a convenience sample of 30 Chinese immigrants who had been diagnosed with NIDDM for at least 1 year. Consenting participants completed paper- and-pencil questionnaires (Diabetes Family-Behavior Checklist II, Diabetes Quality of Life, and MDRTC Knowledge Test) that had been translated and back-translated into Chinese and returned them in stamped, self-addressed envelopes. Results indicated that most of the scale and subscale reliabilities were similar to those published previously. Study participants had received limited diabetes education, reported many problems managing diabetes, especially in terms of social and vocational issues, and reported dissatisfaction with their quality of life. Diabetes-related family supportive behaviors were rated positively indicating the importance of including family members in educational programs.
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Diabetes Mellitus Tipo 2/psicologia , Emigração e Imigração , Qualidade de Vida , Meio Social , Inquéritos e Questionários/normas , Idoso , Idoso de 80 Anos ou mais , China/etnologia , Estudos Transversais , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Projetos Piloto , São FranciscoRESUMO
The purpose of this descriptive study was to examine the relationships between social support and depression and the amount of social support used by 31 widows and 35 widowers. Participants completed the Personal Resource Questionnaire, the Beck Depression Inventory, and a demographic questionnaire. A significant negative relationship was observed between perceived social support and depression. There was no difference in the amount of depression experienced by widows and widowers. There were no significant differences in the two groups' perceptions of support received from their environment or in the number of supportive contacts identified in their social networks.
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Depressão , Apoio Social , Viuvez , Idoso , Feminino , Humanos , MasculinoRESUMO
This article estimates workplace injury costs in the U.S. These costs have been studied in less detail than most injury costs. Our methods, which mostly use regularly published data, produce order-of-magnitude estimates. Overall, workplace injuries cost the U.S. an estimated $140 billion annually. This estimate includes $17 billion in medical and emergency services, $60 billion in lost productivity, $5 billion in insurance costs, and $62 billion in lost quality of life. One sixth of the societal costs result from the 3% of workplace injuries in motor vehicle crashes. Motor vehicle costs per injury are almost 6 times the workplace injury average.
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Acidentes de Trabalho/economia , Ferimentos e Lesões/economia , Absenteísmo , Acidentes de Trabalho/prevenção & controle , Acidentes de Trânsito/economia , Custos e Análise de Custo , Humanos , Estados Unidos , Valor da Vida , Indenização aos Trabalhadores/economia , Ferimentos e Lesões/prevenção & controleRESUMO
Health care workers have been identified as sources of social support for cancer patients. However, little is known about the type of support patients receive from nurses. The primary purpose of this study was to determine if patients perceived differences in how often they received different types of support from nurses. The dimensions of support assessed were based on House's conceptualization of social support as made up of four components: emotional, informational, instrumental, and appraisal. A secondary purpose was to determine how satisfied the patients were with the nursing care they received while hospitalized. Sixty-six patients completed a questionnaire containing a 23-item self-report scale that measured how often they received specific types of support from nurses. The questionnaire also contained a seven-item self-report scale that measured how satisfied they were with the nursing care they received. Patients reported receiving significantly more instrumental and less appraisal support than other types of support (p < 0.008). Satisfaction with nursing care was significantly related to the amount of support they perceived receiving (p < 0.01). Implications for the importance of affirming the personal worth of cancer patient's as a part of routine nursing care are discussed and intervention strategies suggested.
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Neoplasias/enfermagem , Relações Enfermeiro-Paciente , Apoio Social , Adulto , Idoso , Idoso de 80 Anos ou mais , Análise de Variância , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Neoplasias/psicologia , Satisfação do Paciente/estatística & dados numéricos , Fatores Sexuais , Inquéritos e QuestionáriosRESUMO
OBJECTIVES: The American Academy of Pediatrics believes that health education, through office-based counseling, can contribute to childhood injury prevention. This report extends previously published work on the effectiveness of primary care-based counseling and compares the costs and estimated monetary value of the benefits of safety counseling targeting children ages 0 to 4 years. METHODS: We estimate the savings achievable with comprehensive childhood injury prevention counseling organized around the three Framingham Safety Surveys used in The Injury Prevention Program (TIPP) developed by the American Academy of Pediatrics. We verify the estimated savings by comparing them with the effects of pediatrician counseling from separate analyses of the most fully evaluated interventions--in child motor vehicle occupant injuries, burns, and falls. RESULTS: TIPP pediatrician injury counseling sessions between the ages of 0 and 4 years can achieve estimated savings of $880 per child or $80 per visit. If all 19.2 million children ages 0 to 4 years completed TIPP, we estimate that $230 million would be saved annually in medical spending, and injury costs would decline $3.4 billion. each dollar spent on TIPP childhood injury prevention targeting children ages 0 to 4 years returns nearly $13. CONCLUSION: TIPP pediatrician injury counseling is a cost-effective method of preventing childhood injuries and should be more widely adopted.