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Electrocyclic reactions are characterized by the concerted formation and cleavage of both σ and π bonds through a cyclic structure. This structure is known as a pericyclic transition state for thermal reactions and a pericyclic minimum in the excited state for photochemical reactions. However, the structure of the pericyclic geometry has yet to be observed experimentally. We use a combination of ultrafast electron diffraction and excited state wavepacket simulations to image structural dynamics through the pericyclic minimum of a photochemical electrocyclic ring-opening reaction in the molecule α-terpinene. The structural motion into the pericyclic minimum is dominated by rehybridization of two carbon atoms, which is required for the transformation from two to three conjugated π bonds. The σ bond dissociation largely happens after internal conversion from the pericyclic minimum to the electronic ground state. These findings may be transferrable to electrocyclic reactions in general.
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Conformational isomers (conformers) of molecules play a decisive role in biology and organic chemistry. However, experimental methods for investigating chemical reaction dynamics are typically not conformer-sensitive. We report on a gas-phase megaelectronvolt ultrafast electron diffraction investigation of α-phellandrene undergoing an electrocyclic ring-opening reaction. We directly imaged the evolution of a specific set of α-phellandrene conformers into the product isomer predicted by the Woodward-Hoffmann rules in real space and time. Our experimental results are in quantitative agreement with nonadiabatic quantum molecular dynamics simulations, which provide considerable detail of how conformation influences the time scale and quantum efficiency of photoinduced ring-opening reactions.
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Quantum process tomography has become increasingly critical as the need grows for robust verification and validation of candidate quantum processors, since it plays a key role in both performance assessment and debugging. However, as these processors grow in size, standard process tomography becomes an almost impossible task. Here, we present an approach for efficient quantum process tomography that uses a physically motivated ansatz for an unknown quantum process. Our ansatz bootstraps to an effective description for an unknown process on a multi-qubit processor from pairwise two-qubit tomographic data. Further, our approach can inherit insensitivity to system preparation and measurement error from the two-qubit tomography scheme. We benchmark our approach using numerical simulation of noisy three-qubit gates, and show that it produces highly accurate characterizations of quantum processes. Further, we demonstrate our approach experimentally on a superconducting quantum processor, building three-qubit gate reconstructions from two-qubit tomographic data.
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OBJECTIVES: Save the Mothers (STM) operates the toll-free telephone line (TFL) service in nine health facilities in Uganda. The TFL is influential in addressing the first and second delays in seeking care as it connects vulnerable mothers to health facilities at no cost. This study aimed at exploring the experiences of health workers and community members in using the TFL to access maternal and newborn health services in four health facilities in central Uganda. STUDY DESIGN: This phenomenological/qualitative study used focus group discussions (FGDs) to collect data in four health facilities. METHODS: A total of 10 FGDs were conducted; two with health workers, four with women, and another four with both men and women. Each session lasted 45-60 min and had a moderator, observer, and note taker. All discussions were audio-recorded after obtaining consent from the participants. Interviews were transcribed verbatim and translated to English from audio recordings. Data analysis was performed using the thematic analysis using QDA DATA Miner software. RESULTS: The TFL service was pivotal in improving health worker and community relations, relaying timely health advice, ensuring prompt response to obstetric emergencies and facilitated timely referrals. However, the service faced several obstacles: unanswered calls, language differences, poor connectivity/network, and misuse/abuse. CONCLUSION: This study demonstrates the potential of the TFL service in addressing the first and second delay as it allows for timely linkage of vulnerable mothers to health facilities. The TFL enhanced health worker and community relations and facilitated timely referrals and relaying of health advice. Addressing maternal mortality in low-income settings necessitates increased investment and scale up of such high-impact mHealth interventions.
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Servicios de Salud del Niño/organización & administración , Instituciones de Salud/estadística & datos numéricos , Personal de Salud , Accesibilidad a los Servicios de Salud , Servicios de Salud Materna/estadística & datos numéricos , Madres , Derivación y Consulta , Telemedicina/organización & administración , Teléfono , Adulto , Relaciones Comunidad-Institución , Femenino , Grupos Focales , Humanos , Salud del Lactante , Recién Nacido , Masculino , Servicios de Salud Materna/organización & administración , Aceptación de la Atención de Salud , Embarazo , Investigación Cualitativa , UgandaRESUMEN
We report nearly continuous beta-decay-rate measurements of Na-22, Cl-36, Co-60, Sr-90, and Cs-137 over a period of 2.7 years using four Geiger-Müller tubes. We carefully control the ambient pressure and temperature for the detectors, sources, and electronics in order to minimize environmentally-dependent systematic drifts in the measurement chains. We show that the amplitudes of an annual oscillation in the decay rates are consistent with zero to within 0.004%.
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AIM: USEPA Method 1623, or its equivalent, is currently used to monitor for protozoan contamination of surface drinking water sources worldwide. At least three approved staining kits used for detecting Cryptosporidium and Giardia are commercially available. This study focuses on understanding the differences among staining kits used for Method 1623. METHODS AND RESULTS: Merifluor and EasyStain labelling kits were used to monitor Cryptosporidium oocyst and Giardia cyst densities in New York City's raw surface water sources. In the year following a change to the approved staining kits for use with Method 1623, an anomaly was noted in the occurrence of Giardia cysts in New York City's raw surface water. Specifically, Merifluor-stained samples had higher Giardia cyst densities as compared with those stained with EasyStain. Side by side comparison revealed significantly lower fluorescence intensities of Giardia muris as compared with Giardia duodenalis cysts when labelled with EasyStain. CONCLUSIONS: This study showed very poor fluorescence intensity signals by EasyStain on G. muris cysts resulting in lower cyst counts, while Merifluor, with its broader Giardia cyst staining specificity, resulted in higher cyst counts, when using Methods 1623. SIGNIFICANCE AND IMPACT OF THE STUDY: These results suggest that detected Giardia cyst concentrations are dependent on the staining kits used, which can result in a more or less conservative estimation of occurrences and densities of zoonotic Giardia cysts by detecting a broader range of Giardia species/Assemblages.
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Cryptosporidium/aislamiento & purificación , Agua Potable/parasitología , Giardia/aislamiento & purificación , Calidad del Agua , Ciudad de Nueva York , Oocistos/aislamiento & purificación , Abastecimiento de AguaRESUMEN
The Quebec Pain Registry (QPR) is a large research database of patients suffering from various chronic pain (CP) syndromes who were referred to one of five tertiary care centres in the province of Quebec (Canada). Patients were monitored using common demographics, identical clinical descriptors, and uniform validated outcomes. This paper describes the development, implementation, and research potential of the QPR. Between 2008 and 2013, 6902 patients were enrolled in the QPR, and data were collected prior to their first visit at the pain clinic and six months later. More than 90% of them (mean age ± SD: 52.76 ± 4.60, females: 59.1%) consented that their QPR data be used for research purposes. The results suggest that, compared to patients with serious chronic medical disorders, CP patients referred to tertiary care clinics are more severely impaired in multiple domains including emotional and physical functioning. The QPR is also a powerful and comprehensive tool for conducting research in a "real-world" context with 27 observational studies and satellite research projects which have been completed or are underway. It contains data on the clinical evolution of thousands of patients and provides the opportunity of answering important research questions on various aspects of CP (or specific pain syndromes) and its management.
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Dolor Crónico/epidemiología , Dolor Crónico/terapia , Implementación de Plan de Salud , Clínicas de Dolor/estadística & datos numéricos , Manejo del Dolor/métodos , Sistema de Registros , Adulto , Anciano , Dolor Crónico/diagnóstico , Femenino , Implementación de Plan de Salud/métodos , Implementación de Plan de Salud/normas , Humanos , Masculino , Persona de Mediana Edad , Dimensión del Dolor , Quebec/epidemiología , Sistema de Registros/normas , Sistema de Registros/estadística & datos numéricos , Estudios Retrospectivos , Encuestas y Cuestionarios , Factores de TiempoRESUMEN
BACKGROUND: Pain expectancy may be an important variable that has been found to influence the effectiveness of treatments for pain. Much of the literature supports a self-fulfilment perspective where expectations for pain relief predict the actual pain experienced. However, in conditions such as neuropathic pain (NeP) where pain relief is difficult to attain, expectations for pain relief could be unrealistic. The objective of this study was to investigate the relationship between realistic/unrealistic expectations and 6-month, post-treatment outcomes. METHODS: We performed a retrospective analysis of a large cohort of patients with NeP (n = 789) attending tertiary care centres to determine the association between unrealistic (both positive and negative) and realistic expectations with outcomes after multidisciplinary treatment. An expectation variable with three categories was calculated: realistic expectations were those whose expected reduction in pain was similar to the observed mean group reduction in pain, while optimistic and pessimistic expectations were those who over- or under-estimated the expected response to treatment, respectively. The association between baseline realistic/unrealistic expectations and 6-month pain-related disability, catastrophizing and psychological distress was assessed. RESULTS: Univariable analyses suggested that realistic expectations were associated with lower levels of disability, catastrophizing and psychological distress, compared to unrealistic expectations. However, after adjustment for baseline symptom severity, multivariable analysis revealed that patients with optimistic expectations had lower levels of disability, than those with realistic expectations. Those with pessimistic expectations had higher levels of catastrophizing and psychological distress at follow-up. CONCLUSIONS: These findings are largely congruent with the self-fulfilment perspective to expectations. SIGNIFICANCE: This study defined realistic pain expectations with patient data. Examining the relationship between expectations between pain and disability in a large cohort of patients with neuropathic pain.
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Analgesia/psicología , Catastrofización/psicología , Neuralgia/psicología , Adulto , Anciano , Personas con Discapacidad , Femenino , Humanos , Masculino , Persona de Mediana Edad , Manejo del Dolor , Dimensión del Dolor/psicología , Estudios Retrospectivos , Resultado del TratamientoRESUMEN
Herein we investigate a (001)-oriented GaAs1-xBix/GaAs structure possessing Bi surface droplets capable of catalysing the formation of nanostructures during Bi-rich growth, through the vapour-liquid-solid mechanism. Specifically, self-aligned "nanotracks" are found to exist trailing the Bi droplets on the sample surface. Through cross-sectional high-resolution transmission electron microscopy the nanotracks are revealed to in fact be elevated above surface by the formation of a subsurface planar nanowire, a structure initiated mid-way through the molecular-beam-epitaxy growth and embedded into the epilayer, via epitaxial overgrowth. Electron microscopy studies also yield the morphological, structural, and chemical properties of the nanostructures. Through a combination of Bi determination methods the compositional profile of the film is shown to be graded and inhomogeneous. Furthermore, the coherent and pure zincblende phase property of the film is detailed. Optical characterisation of features on the sample surface is carried out using polarised micro-Raman and micro-photoluminescence spectroscopies. The important light producing properties of the surface nanostructures are investigated through pump intensity-dependent micro-PL measurements, whereby relatively large local inhomogeneities are revealed to exist on the epitaxial surface for important optical parameters. We conclude that such surface effects must be considered when designing and fabricating optical devices based on GaAsBi alloys.
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Electronic and optical properties of InAs/GaAs nanostructures grown by the droplet epitaxy method are studied. Carrier states were determined by k · p theory including effects of strain and In gradient concentration for a model geometry. Wavefunctions are highly localized in the dots. Coulomb and exchange interactions are studied and we found the system is in the strong confinement regime. Microphotoluminescence spectra and lifetimes were calculated and compared with measurements performed on a set of quantum rings in a single sample. Some features of spectra are in good agreement.
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BACKGROUND: The management of chronic pain, including neuropathic pain (NeP), is a major public health issue. However, there is a paucity of data evaluating pain management strategies in real-life settings. OBJECTIVE: To inform policy makers about the economic value of managing chronic NeP in academic centres by conducting a subeconomic assessment of a Canadian multicentre cohort study aimed at determining the long-term outcomes of the management of chronic NeP in academic pain centres. Specific questions regarding the economic value of this type of program were answered by a subset of patients to provide further information to policy makers. METHODS: Baseline demographic information and several pain-related measurements were collected at baseline, three, six and 12 months in the main study. A resource use questionnaire aimed at determining NeP-related costs and the EuroQoL-5 Dimension were collected in the subset study from consenting patients. Statistical analyses were conducted to compare outcomes over time and according to responder status. RESULTS: A total of 298 patients were evaluated in the present economic evaluation. The mean (± SD) age of the participants was 53.7±14.0 years, and 56% were female. At intake, the mean duration of NeP was >5 years. Statistically significant improvements in all pain and health-related quality of life outcomes were observed between the baseline and one-year visits. Use decreased over time for many health care resources (eg, visits to the emergency room decreased by one-half), which resulted in overall cost savings. CONCLUSION: The results suggest that increased access to academic pain centres should be facilitated in Canada.
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Costos de la Atención en Salud , Neuralgia , Manejo del Dolor/economía , Manejo del Dolor/métodos , Calidad de Vida/psicología , Adulto , Anciano , Anciano de 80 o más Años , Canadá , Estudios de Cohortes , Evaluación de la Discapacidad , Femenino , Humanos , Masculino , Persona de Mediana Edad , Neuralgia/economía , Neuralgia/psicología , Neuralgia/terapia , Dimensión del Dolor , Satisfacción del Paciente , Estadísticas no Paramétricas , Encuestas y Cuestionarios , Adulto JovenRESUMEN
We describe an experimental setup for making precision measurements of relative ß-decay rates of (22)Na, (36)Cl, (54)Mn, (60)Co, (90)Sr, (133)Ba, (137)Cs, (152)Eu, and (154)Eu. The radioactive samples are mounted in two automated sample changers that sequentially position the samples with high spatial precision in front of sets of detectors. The set of detectors for one sample changer consists of four Geiger-Müller (GM) tubes and the other set of detectors consists of two NaI scintillators. The statistical uncertainty in the count rate is few times 0.01% per day for the GM detectors and about 0.01% per hour on the NaI detectors. The sample changers, detectors, and associated electronics are housed in a sealed chamber held at constant absolute pressure, humidity, and temperature to isolate the experiment from environmental variations. The apparatus is designed to accumulate statistics over many years in a regulated environment to test recent claims of small annual variations in the decay rates. We demonstrate that absent this environmental regulation, uncontrolled natural atmospheric pressure variations at our location would imprint an annual signal of 0.1% on the Geiger-Müller count rate. However, neither natural pressure variations nor plausible indoor room temperature variations cause a discernible influence on our NaI scintillator detector count rate.
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The global regulatory landscape regarding the medical use of cannabis and cannabinoids is changing rapidly. This has considerable impact on health care professionals who currently receive little or no education on issues regarding medical cannabis. We propose a 'cannabis curriculum' that covers the spectrum of historical, botanical, physiological, clinical and legal issues to allow health care professionals to engage in meaningful discussions with their patients and colleagues around this stigmatized and controversial subject.
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Cannabinoides/uso terapéutico , Educación Médica , Marihuana Medicinal/uso terapéutico , Fitoterapia , Curriculum , HumanosRESUMEN
We report on biological performance of organic nanoparticles formed by a simple method based on rapid solvent removal from a volatile microemulsion. The particular focus of the study was on testing the suitability of the method for substances soluble in partially water-miscible organic solvents as well as on evaluating the therapeutic activity of the resultant nanoparticles. Curcumin was employed as a model for hydrophobic drug, and, as it is soluble in water-miscible organic solvents, it was successfully incorporated into a new cyclopentanone-water microemulsion system. During rapid solvent removal by spray-drying, the nanometric droplets of the microemulsion were converted into nanoparticles containing amorphous curcumin with the average size of 20.2±3.4 nm, having ζ potential of -36.2 ±1.8 mV. These nanoparticles were dispersible in water and retained the high loading of the active substance. The therapeutic activity of the resulting nanoparticles was demonstrated in a pancreatic cancer cell line Panc-1. The effective concentration for reducing the metabolic activity was found to be 11.5 µM for nanoparticles compared with 19.5 µM for free curcumin.
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We report on the mechanism of strain-influenced quantum well (QW) thickness reduction in GaN/AlN short-period superlattices grown by plasma-assisted molecular beam epitaxy. Density functional theory was used to support the idea of a thermally activated exchange mechanism between Al adatoms and Ga surface atoms that is influenced by the strain state of the GaN QWs. These ab initio calculations support our experimentally observed reduction in QW thickness for different intrinsic strains.
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Pulse reshaping effects that give rise to fast and slow light phenomena are inextricably linked to the dynamics of energy exchange between the pulse and the propagation medium. Energy that is dissipated from the pulse can no longer participate in this exchange process, but previous methods of calculating real-time dissipation are not valid for extended propagation media. We present a method for calculating real-time dissipation that is valid for electromagnetic pulse propagation in extended media. This method allows one to divide the energy stored in an extended medium into the portion that can be later transmitted out of the medium, and that portion which must be lost to either dissipation or reflection.
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The structural and optical properties of GaAs1-xBix quantum wells (QWs) symmetrically clad by GaAs barriers with and without additional confining AlGaAs layers are studied. It is shown that a GaAs/GaAs1-xBix/GaAs QW with x ~ 4% and well width of ~ 4 nm grown by molecular beam epitaxy demonstrates efficient photoluminescence (PL) that becomes significantly more thermally stable when a cladding AlGaAs layer is added to the QW structure. The PL behavior for temperatures between 10 and 300 K and for excitation intensities varying by seven orders of magnitude can be well described in terms of the dynamics of excitons including carrier capture in the QW layer, thermal emission and diffusion into the cladding barriers. Understanding the role of these processes in the luminescence of dilute GaAs1-xBix QW structures facilitates the creation of highly efficient devices with reduced thermal sensitivity and low threshold current.
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AIMS: This study developed and systematically evaluated performance and limit of detection of an off-the-slide genotyping procedure for both Cryptosporidium oocysts and Giardia cysts. METHODS AND RESULTS: Slide standards containing flow-sorted (oo)cysts were used to evaluate the off-the-slide genotyping procedure by microscopy and PCR. Results show approximately 20% of cysts and oocysts are lost during staining. Although transfer efficiency from the slide to the PCR tube could not be determined by microscopy, it was observed that the transfer process aided in the physical lysis of the (oo)cysts likely releasing DNA. PCR detection rates for a single event on a slide were 44% for Giardia and 27% for Cryptosporidium, and a minimum of five cysts and 20 oocysts are required to achieve a 90% PCR detection rate. A Poisson distribution analysis estimated the relative PCR target densities and limits of detection, it showed that 18 Cryptosporidium and five Giardia replicates are required for a 95% probability of detecting a single (oo)cyst on a slide. CONCLUSIONS: This study successfully developed and evaluated recovery rates and limits of detection of an off-the-slide genotyping procedure for both Cryptosporidium and Giardia (oo)cysts from the same slide. SIGNIFICANCE AND IMPACT OF THE STUDY: This off-the-slide genotyping technique is a simple and low cost tool that expands the applications of US EPA Method 1623 results by identifying the genotypes and assemblages of the enumerated Cryptosporidium and Giardia. This additional information will be useful for microbial risk assessment models and watershed management decisions.
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Cryptosporidium/aislamiento & purificación , Técnicas de Genotipaje , Giardia/aislamiento & purificación , Cryptosporidium/genética , Cryptosporidium/crecimiento & desarrollo , Citometría de Flujo , Giardia/genética , Giardia/crecimiento & desarrollo , Oocistos/citología , Reacción en Cadena de la Polimerasa , Estados UnidosRESUMEN
The hazy world of "medical marijuana" continues to cry out for clear data on which to base medical decision making and rational policy design. In this issue of Clinical Pharmacology & Therapeutics, Abrams and colleagues report that vaporized cannabis does not meaningfully affect opioid plasma levels and may even augment the efficacy of oxycodone and morphine in patients with chronic non-cancer pain. This Commentary considers the implications of this work for clinical practice and further research initiatives.