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People with diabetes-related foot ulcers (DFUs) need to perform self-care consistently over many months to promote healing and to mitigate risks of hospitalisation and amputation. However, during that time, improvement in their DFU can be hard to detect. Hence, there is a need for an accessible method to self-monitor DFUs at home. We developed a new mobile phone app, "MyFootCare", to self-monitor DFU healing progression from photos of the foot. The aim of this study is to evaluate the engagement and perceived value of MyFootCare for people with a plantar DFU over 3 months' duration. Data are collected through app log data and semi-structured interviews (weeks 0, 3, and 12) and analysed through descriptive statistics and thematic analysis. Ten out of 12 participants perceive MyFootCare as valuable to monitor progress and to reflect on events that affected self-care, and seven participants see it as potentially valuable to enhance consultations. Three app engagement patterns emerge: continuous, temporary, and failed engagement. These patterns highlight enablers for self-monitoring (such as having MyFootCare installed on the participant's phone) and barriers (such as usability issues and lack of healing progress). We conclude that while many people with DFUs perceive app-based self-monitoring as valuable, actual engagement can be achieved for some but not for all people because of various facilitators and barriers. Further research should target improving usability, accuracy and sharing with healthcare professionals and test clinical outcomes when using the app.
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Teléfono Celular , Diabetes Mellitus , Pie Diabético , Aplicaciones Móviles , Humanos , Pie Diabético/diagnóstico , Pie , Amputación QuirúrgicaRESUMEN
We use transmission optical microscopy to observe cyclopentane hydrate growth in sub-mm, open glass capillaries, mimicking cylindrical pores. The capillary is initially loaded with water and the guest fluid (cyclopentane) and thus possesses three menisci, that between water and cyclopentane (CP) in the middle and two menisci with the vapors at the ends. At temperatures T below the equilibrium temperature Teq ≈ 7 °C, the hydrate nucleates on the water-CP meniscus, rapidly coating it with an immobile, polycrystalline crust. Continued movement of the other two menisci provides insights into hydrate growth mechanisms, via the consumption and displacement of the fluids. On water-wet glass, the subsequent growth consists of a hydrate "halo" creeping with an underlying water layer on the glass on the CP side of the meniscus. Symmetrically, on CP-wet glass (silane-treated), a halo and a CP layer grow on the water side of the interface. No halo is observed on intermediate wet glass. The halo consists of an array of large monocrystals, over a thick water layer at low supercooling (ΔT = Teq - T below 5 K), and a finer, polycrystalline texture over a thinner water layer at higher ΔT. Furthermore, the velocity varies as ΔTα, with α ≈ 2.7, making the early stages of growth very similar to gas hydrate crusts growing over water-guest interfaces. Beyond a length in the millimeter range, the halo and its water layer abruptly decelerate and thin down to submicron thickness. The halo passes through the meniscus with the vapor without slowing down or change of texture. A model of the mass balance of the fluids helps rationalize all of these observations.
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Round glass capillaries are a basic tool in soft-matter science, but often are shunned due to the astigmatism they introduce in micrographs. Here, we show how refraction in a capillary can be a help instead of a hindrance to obtain precise and sensitive information on two important interfacial properties: the contact angle of two immiscible fluids and the presence of thin films on the capillary wall. Understanding optical cusps due to refraction allows direct mesurement of the inner diameter of a capillary at the meniscus, which, with the height of the meniscus cap, determines the contact angle. The meniscus can thus be measured without intrusive additives to enhance visibility, such as dyes or calibrated particles, in uniform, curved, or even tapered capillaries or under demanding conditions not accessible by conventional methods, such as small volumes (µL), high temperatures, or high pressures. We further elicit the conditions for strong internal reflection on the inner capillary wall, involving the wall and fluid refractive indices and the wall thickness, and show how to choose the capillary section to detect thin (submicron) layers on the wall, by the contribution of total internal reflection to the cusps. As examples, we report the following: (i) CO2-water or -brine contact angles at glass interfaces, measured at temperatures and pressures up to 200 °C and 600 bar, revealing an effect apparently so far unreported-the decrease in the water-wet character of glass, due to dissolved salts in brine, is strongly reduced at high temperatures, where contact angles converge toward the values in pure water; (ii) A tenuous gas hydrate layer growing from the water-guest contact line on glass, invisible in transmission microscopy but prominent in the cusps due to total internal reflection.
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A modified Stöber method is used to synthesize spherical core-shell silica nanoparticles (NPs) with an external surface functionalized by amino groups and with an average size around 50 nm. Fluorescent dyes and photosensitizers of singlet oxygen were fixed, either separately or conjointly, respectively in the core or in the shell. Rhodamines were encapsulated in the core with relatively high fluorescence quantum yields (Φfl ≥ 0.3), allowing fluorescence tracking of the particles. Various photosensitizers of singlet oxygen (PS) were covalenty coupled to the shell, allowing singlet oxygen production. The stability of NP suspensions strongly deteriorated upon grafting the PS, affecting their apparent singlet oxygen quantum yields. Agglomeration of NPs depends both on the type and on the amount of grafted photosensitizer. New, lab-made, halogenated 4,4-difluoro-4-bora-3a,4a-diaza-s-indacenes (BODIPY) grafted to the NPs achieved higher singlet oxygen quantum yields (ΦΔ â¼ 0.35-0.40) than Rose Bengal (RB) grafted NPs (ΦΔ â¼ 0.10-0.27). Finally, we combined both fluorescence and PS functions in the same NP, namely a rhodamine in the silica core and a BODIPY or RB grafted in the shell, achieving the performance Φfl â¼ 0.10-0.20, ΦΔ â¼ 0.16-0.25 with a single excitation wavelength. Thus, proper choice of the dyes, of their concentrations inside and on the NPs and the grafting method enables fine-tuning of singlet oxygen production and fluorescence emission.
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Multiple myeloma (MM) is a haematological malignancy characterised by the clonal proliferation of plasma cells in the bone marrow. More than 80% of patients with MM display evidence of myeloma bone disease (MBD), characterised by the formation of osteolytic lesions throughout the axial and appendicular skeleton. MBD significantly increases the risk of skeletal-related events such as pathologic fracture, spinal cord compression and hypercalcaemia. MBD is the result of MM plasma cells-mediated activation of osteoclast activity and suppression of osteoblast activity. Bisphosphonates (BP), pyrophosphate analogues with high bone affinity, are the only pharmacological agents currently recommended for the treatment and prevention of MBD and remain the standard of care. Pamidronate and zoledronic acid are the most commonly used BP to treat MBD. Although generally safe, frequent high doses of BP are associated with adverse events such as renal toxicity and osteonecrosis of the jaw. As such, optimal duration and dosing of BP therapy is required in order to minimise BP-associated adverse events. The following guidelines provide currently available evidence for the adoption of a tailored approach when using BP for the management of MBD.
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Conservadores de la Densidad Ósea/efectos adversos , Neoplasias Óseas/tratamiento farmacológico , Difosfonatos/efectos adversos , Mieloma Múltiple/tratamiento farmacológico , Guías de Práctica Clínica como Asunto , Osteonecrosis de los Maxilares Asociada a Difosfonatos/etiología , Conservadores de la Densidad Ósea/administración & dosificación , Neoplasias Óseas/complicaciones , Neoplasias Óseas/prevención & control , Huesos , Difosfonatos/administración & dosificación , Medicina Basada en la Evidencia , Humanos , Enfermedades Renales/etiología , Mieloma Múltiple/complicaciones , Mieloma Múltiple/prevención & control , Radiografía , Factores de RiesgoRESUMEN
Waldenström macroglobulinaemia (WM) is an indolent B-cell malignancy characterised by the presence of immunoglobulin M (IgM) paraprotein and bone marrow infiltration by clonal small B lymphocytes, plasmacytoid lymphocytes and plasma cells. The symptoms of WM are protean, often follow an asymptomatic phase and may include complications related to the paraneoplastic effects of IgM paraprotein. The revised 2016 World Health Organization classification includes the MYD88 L265P mutation, which is seen in >90% of cases, within the diagnostic criteria for WM. While treatment of WM has often been considered together with other indolent B cell lymphomas, there are unique aspects of WM management that require specific care. These include the unreliability of IgM and paraprotein measurements in monitoring patients prior to and after treatment, the lack of correlation between disease burden and symptoms and rituximab-induced IgM flare. Moreover, while bendamustine and rituximab has recently been approved for reimbursed frontline use in WM in Australia, other regimens, including ibrutinib- and bortezomib-based treatments, are not funded, requiring tailoring of treatment to the regional regulatory environment. The Medical and Scientific Advisory Group of the Myeloma Foundation Australia has therefore developed clinical practice guidelines with specific recommendations for the work-up and therapy of WM to assist Australian clinicians in the management of this disease.
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Antineoplásicos/uso terapéutico , Inmunoglobulina M/sangre , Macroglobulinemia de Waldenström/tratamiento farmacológico , Adenina/análogos & derivados , Comités Consultivos , Australia , Clorhidrato de Bendamustina/uso terapéutico , Médula Ósea/patología , Bortezomib/uso terapéutico , Humanos , Mutación , Factor 88 de Diferenciación Mieloide/genética , Piperidinas , Células Plasmáticas/patología , Guías de Práctica Clínica como Asunto , Pirazoles/uso terapéutico , Pirimidinas/uso terapéutico , Rituximab/uso terapéutico , Sociedades Médicas , Macroglobulinemia de Waldenström/diagnósticoRESUMEN
Human plasmacytoid dendritic cells (pDCs) were considered to be a phenotypically and functionally homogeneous cell population; however, recent analyses indicate potential heterogeneity. This is of major interest, given their importance in the induction of anti-viral responses and their role in creating immunologically permissive environments for human malignancies. For this reason, we investigated the possible presence of human pDC subsets in blood and bone marrow, using unbiased cell phenotype clustering and functional studies. This defined two major functionally distinct human pDC subsets, distinguished by differential expression of CD2. The CD2(hi) and CD2(lo) pDCs represent discontinuous subsets, each with hallmark pDC functionality, including interferon-alpha production. The rarer CD2(hi) pDC subset demonstrated a significant survival advantage over CD2(lo) pDC during stress and upon exposure to glucocorticoids (GCs), which was associated with higher expression of the anti-apoptotic molecule BCL2. The differential sensitivity of these two human pDC subsets to GCs is demonstrated in vivo by a relative increase in CD2(hi) pDC in multiple myeloma patients treated with GCs. Hence, the selective apoptosis of CD2(lo) pDC during stress represents a novel mechanism for the control of innate responses.
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Antígenos CD2/metabolismo , Células Dendríticas/metabolismo , Estrés Fisiológico , Apoptosis/efectos de los fármacos , Médula Ósea/metabolismo , Membrana Celular/efectos de los fármacos , Membrana Celular/metabolismo , Supervivencia Celular/efectos de los fármacos , Células Dendríticas/citología , Células Dendríticas/efectos de los fármacos , Glucocorticoides/farmacología , Humanos , Ligandos , Ganglios Linfáticos/metabolismo , Proteínas Proto-Oncogénicas c-bcl-2/metabolismo , Receptores Inmunológicos/metabolismo , Estrés Fisiológico/efectos de los fármacos , Receptores Toll-Like/metabolismoRESUMEN
Despite evidence from a number of Earth systems that abrupt temporal changes known as regime shifts are important, their nature, scale and mechanisms remain poorly documented and understood. Applying principal component analysis, change-point analysis and a sequential t-test analysis of regime shifts to 72 time series, we confirm that the 1980s regime shift represented a major change in the Earth's biophysical systems from the upper atmosphere to the depths of the ocean and from the Arctic to the Antarctic, and occurred at slightly different times around the world. Using historical climate model simulations from the Coupled Model Intercomparison Project Phase 5 (CMIP5) and statistical modelling of historical temperatures, we then demonstrate that this event was triggered by rapid global warming from anthropogenic plus natural forcing, the latter associated with the recovery from the El Chichón volcanic eruption. The shift in temperature that occurred at this time is hypothesized as the main forcing for a cascade of abrupt environmental changes. Within the context of the last century or more, the 1980s event was unique in terms of its global scope and scale; our observed consequences imply that if unavoidable natural events such as major volcanic eruptions interact with anthropogenic warming unforeseen multiplier effects may occur.
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Cambio Climático/historia , Modelos Teóricos , Clima , Historia del Siglo XX , Modelos Estadísticos , Análisis de Componente Principal , Temperatura , Erupciones VolcánicasRESUMEN
We report synthesis, characterisation and molecular modelling of a new fluorescent cyclotriveratrylene probe for acetylcholine in aqueous media, with emission around 430 nm thanks to extended conjugation. The probe discriminates acetylcholine from choline, with respective binding constants 540 and 240 M(-1) in PBS buffered saline solution, an order of magnitude improvement over the previous best performance. Dynamic light scattering and transmission electron microscopy show the new probe self-assembles in ca. 5 nm diameter particles in PBS medium. Molecular modelling suggests that the high fluorescence quantum yield of the probe, 20% in aqueous media, is due to features of the molecular arrangement in the nano-particles, contributing both to exposure of the complexation site and to shielding of the fluorescent π system from quenching by water. Titration data for other quaternary ammoniums and modelling indicate that recognition of acetylcholine vs. choline depends on specific electrostatic interactions, and to a lesser extent on exclusion of water by hydrophobic-hydrophilic segregation. Probe-substrate interactions enhance the fluorescence of the probe by shielding against water and by flattening the π system.
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Acetilcolina/análisis , Calixarenos/química , Colorantes Fluorescentes/química , Tampones (Química) , Colina/análisis , Simulación de Dinámica Molecular , Nanopartículas , Fosfatos , Cloruro de Sodio , SolucionesRESUMEN
The transfer of membrane proteins between cells during contact, known as trogocytosis, can create novel cells with a unique phenotype and altered function. We demonstrate that trogocytosis is more common in multiple myeloma (MM) than chronic lymphocytic leukemia and Waldenstrom macroglobulinaemia; that T cells are more probable to be recipients than B or natural killer cells; that trogocytosis occurs independently of either the T-cell receptor or HLA compatibility; and that after trogocytosis, T cells with acquired antigens can become novel regulators of T-cell proliferation. We screened 168 patients with MM and found that CD86 and human leukocyte antigen G (HLA-G) were antigens commonly acquired by T cells from malignant plasma cells. CD3+ CD86acq+ and CD3+ HLA-Gacq+ cells were more prevalent in bone marrow than peripheral blood samples. The presence of either CD86 or HLA-G on malignant plasma cells was associated with a poor prognosis. CD38++ side population cells expressed HLA-G, suggesting that these putative myeloma stem cells could generate immune tolerance. HLA-G+ T cells had a regulatory potency similar to natural Tregs, thus providing another novel mechanism for MM to avoid effective immune surveillance.
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Antígeno B7-2/inmunología , Antígenos HLA-G/inmunología , Leucemia Linfocítica Crónica de Células B/metabolismo , Mieloma Múltiple/metabolismo , Células Plasmáticas/inmunología , Macroglobulinemia de Waldenström/metabolismo , Linfocitos B/inmunología , Linfocitos B/metabolismo , Biomarcadores/análisis , Membrana Celular/inmunología , Membrana Celular/metabolismo , Proliferación Celular , Humanos , Tolerancia Inmunológica , Células Asesinas Naturales/inmunología , Células Asesinas Naturales/metabolismo , Leucemia Linfocítica Crónica de Células B/inmunología , Leucemia Linfocítica Crónica de Células B/mortalidad , Mieloma Múltiple/inmunología , Mieloma Múltiple/mortalidad , Especificidad de Órganos , Células Plasmáticas/metabolismo , Pronóstico , Transporte de Proteínas/inmunología , Tasa de Supervivencia , Linfocitos T/inmunología , Linfocitos T/metabolismo , Macroglobulinemia de Waldenström/inmunología , Macroglobulinemia de Waldenström/mortalidadRESUMEN
Honeycomb-structured porous polymer films based on photosensitizer-grafted polystyrene are prepared through the breath figure process. Rose Bengal (RB) photosensitizer is first attached to a well-defined poly(styrene-stat-4-vinylbenzyl chloride) statistical copolymer, synthesized by nitroxide-mediated radical polymerization. The RB grafted poly(styrene-stat-4-vinylbenzyl chloride) (ca. 20,000 g mol(-1) molar mass, 1.2 dispersity) leads to porous polymer films, with a hexagonal pore pattern, while a simple mixture of poly(styrene-stat-4-vinylbenzyl chloride) and the insoluble RB photosensitizer produced unstructured, nonporous films. The RB-grafted honeycomb films, compared with the corresponding nonporous flat films, are more efficient for oxidation of organic molecules via singlet oxygen production at a liquid/solid interface. The oxidations of 1,5-dihydroxynaphthalene to juglone and α-terpinene to ascaridole are followed in ethanol in the presence of both types of films. Oxidation of the organic molecules is a factor 5 greater with honeycomb compared to the nonporous films. This gain is ascribed to two factors: the specific location of the polar photosensitizer at the film interface and the greater exchange surface, as revealed by fluorescence and scanning electron microscopies.
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Fármacos Fotosensibilizantes/química , Poliestirenos/química , Rosa Bengala/química , Estructura Molecular , Tamaño de la Partícula , Procesos Fotoquímicos , Poliestirenos/síntesis química , Porosidad , Propiedades de SuperficieRESUMEN
Certain species of marine microalgae produce potent biotoxins that pose a risk to human health if contaminated seafood is consumed, particularly filter feeding bivalve shellfish. In regions where this is likely to occur water and seafood produce are regularly monitored for the presence of harmful algal cells and their associated toxins, but the current approach is flawed by a lengthy delay before results are available to local authorities. Quantitative Polymerase Chain Reaction (qPCR) can be used to measure phytoplankton DNA sequences in a shorter timeframe, however it is not currently used in official testing practices. In this study, samples were collected almost weekly over six months from three sites within a known HAB hotspot, St Austell Bay in Cornwall, England. The abundance of algal cells in water was measured using microscopy and qPCR, and lipophilic toxins were quantified in mussel flesh using LC-MS/MS, focusing on the okadaic acid group. An increase in algal cell abundance occurred alongside an increase in the concentration of okadaic acid group toxins in mussel tissue at all three study sites, during September and October 2021. This event corresponded to an increase in the measured levels of Dinophysis accuminata DNA, measured using qPCR. In the following spring, the qPCR detected an increase in D. accuminata DNA levels in water samples, which was not detected by microscopy. Harmful algal species belonging to Alexandrium spp. and Pseudo-nitzschia spp. were also measured using qPCR, finding a similar increase in abundance in Autumn and Spring. The results are discussed with consideration of the potential merits and limitations of the qPCR technique versus conventional microscopy analysis, and its potential future role in phytoplankton surveillance under the Official Controls Regulations pertaining to shellfish.
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Dinoflagelados , Microalgas , Humanos , Microalgas/genética , Cromatografía Liquida , Ácido Ocadaico , Espectrometría de Masas en Tándem , Mariscos , Alimentos Marinos , Fitoplancton/genética , Reacción en Cadena de la PolimerasaRESUMEN
T cells contribute to host-tumor interactions in patients with monoclonal gammopathies. Expansions of CD8(+)CD57(+) T-cell receptor Vbeta-positive (TCRVbeta(+))-restricted cytotoxic T-cell (CTL) clones are found in 48% of patients with multiple myeloma and confer a favorable prognosis. We now report that CTL clones with varying TCRVbeta repertoire are present in 70% of patients with Waldenström macroglobulinemia (WM; n = 20). Previous nucleoside analog (NA) therapy, associated with increased incidence of transformation to aggressive lymphoma, significantly influenced the presence of TCRVbeta expansions (chi(2) = 11.6; P < .001), as 83% of patients without (n = 6) and only 7% with (n = 14) TCRVbeta expansions had received NA. Clonality of CD3(+)CD8(+)CD57(+)TCRVbeta(+)-restricted CTLs was confirmed by TCRVbeta CDR3 size analysis and direct sequencing. The differential expression of CD3(+)CD8(+)CD57(+)TCRVbeta(+) cells was profiled using DNA microarrays and validated at mRNA and protein level. By gene set enrichment analysis, CTL clones expressed not only genes from cytotoxic pathways (GZMB, PRF1, FGFBP2) but also genes that suppress apoptosis, inhibit proliferation, arrest cell-cycle G1/S transition, and activate T cells (RAS, CSK, and TOB pathways). Proliferation tracking after stimulation confirmed their anergic state. Our studies demonstrate the incidence, NA sensitivity, and nature of clonal CTLs in WM and highlight mechanisms that cause anergy in these cells.
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Linfocitos T CD8-positivos/metabolismo , Anergia Clonal , Nucleósidos/uso terapéutico , Macroglobulinemia de Waldenström/sangre , Adulto , Anciano , Anciano de 80 o más Años , Animales , Antígenos CD/biosíntesis , Antígenos CD/inmunología , Linfocitos T CD8-positivos/inmunología , Femenino , Perfilación de la Expresión Génica , Regulación Neoplásica de la Expresión Génica/efectos de los fármacos , Regulación Neoplásica de la Expresión Génica/genética , Regulación Neoplásica de la Expresión Génica/inmunología , Humanos , Masculino , Ratones , Persona de Mediana Edad , Proteínas de Neoplasias/biosíntesis , Proteínas de Neoplasias/genética , Proteínas de Neoplasias/inmunología , Análisis de Secuencia por Matrices de Oligonucleótidos , ARN Mensajero/biosíntesis , ARN Mensajero/genética , ARN Mensajero/inmunología , ARN Neoplásico/biosíntesis , ARN Neoplásico/genética , ARN Neoplásico/inmunología , Receptores de Antígenos de Linfocitos T alfa-beta/genética , Receptores de Antígenos de Linfocitos T alfa-beta/inmunología , Receptores de Antígenos de Linfocitos T alfa-beta/metabolismo , Macroglobulinemia de Waldenström/tratamiento farmacológico , Macroglobulinemia de Waldenström/genética , Macroglobulinemia de Waldenström/inmunologíaRESUMEN
Nursing training for an Intensive Care Unit (ICU) is a resource intensive process. High demands are made on staff, students and physical resources. Interactive, 3D computer simulations, known as virtual worlds, are increasingly being used to supplement training regimes in the health sciences; especially in areas such as complex hospital ward processes. Such worlds have been found to be very useful in maximising the utilisation of training resources. Our aim is to design and develop a novel virtual world application for teaching and training Intensive Care nurses in the approach and method for shift handover, to provide an independent, but rigorous approach to teaching these important skills. In this paper we present a virtual world simulator for students to practice key steps in handing over the 24/7 care requirements of intensive care patients during the commencing first hour of a shift. We describe the modelling process to provide a convincing interactive simulation of the handover steps involved. The virtual world provides a practice tool for students to test their analytical skills with scenarios previously provided by simple physical simulations, and live on the job training. Additional educational benefits include facilitation of remote learning, high flexibility in study hours and the automatic recording of a reviewable log from the session. To the best of our knowledge, we believe this is a novel and original application of virtual worlds to an ICU handover process. The major outcome of the work was a virtual world environment for training nurses in the shift handover process, designed and developed for use by postgraduate nurses in training.
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Simulación por Computador , Unidades de Cuidados Intensivos/organización & administración , Personal de Enfermería en Hospital/organización & administración , Pase de Guardia/organización & administración , Humanos , Capacitación en ServicioRESUMEN
Environmentally sensitive molecular rotors are widely used to probe the local molecular environment in e.g. polymer solutions, polymer glasses, and biological systems. These applications make it important to understand its fluorescence properties in the vicinity of a solid surface, since fluorescence microscopy generically employs cover slides, and measurements are often done in its immediate vicinity. Here, we use a confocal microscope to investigate the fluorescence of (4-DASPI) in glycerol/water solutions close to the interface using hydrophilic or hydrophobic cover slips. Despite the dye's high solubility in water, the observed lengthening of the fluorescence lifetime close to the hydrophobic surface, implies a surprising affinity of the dye with the surface. Because the homogeneous solution and the refractive index mismatch reduces the optical sectioning power of the microscope, we quantify the affinity with the help of a simple model of the signal vs. depth of focus, exhibiting surface and bulk contributions. The model reduces artefacts due to refractive index mismatch, as supported by Monte Carlo ray tracing simulations.
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Colorantes Fluorescentes , Agua , Colorantes Fluorescentes/química , Adsorción , Agua/química , Sondas Moleculares , Interacciones Hidrofóbicas e Hidrofílicas , Propiedades de SuperficieRESUMEN
We evaluated whether near-infrared spectroscopy (NIRS) measurement from the flank correlates with renal vein saturation in children undergoing cardiac catheterization. Thirty-seven patients <18 years of age were studied. A NIRS sensor was placed on the flank, and venous oxygen saturations were measured from the renal vein and the inferior vena cava (IVC). There was a strong correlation between flank NIRS values (rSO(2)) and renal vein saturation (r = 0.821, p = 0.002) and IVC saturation (r = 0.638, p = 0.004) in children weighing ≤ 10 kg. In children weighing > 10 kg, there was no correlation between rSO(2) and renal vein saturation (r = 0.158, p = 0.57) or IVC saturation (r = -0.107, p = 0.67). Regional tissue oxygenation as measured by flank NIRS correlates well with both renal vein and IVC oxygen saturations in children weighing <10 kg undergoing cardiac catheterization, but not in larger children.
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Cardiopatías/metabolismo , Riñón/metabolismo , Consumo de Oxígeno , Oxígeno/metabolismo , Espectroscopía Infrarroja Corta/métodos , Niño , Preescolar , Femenino , Humanos , Lactante , Recién Nacido , Masculino , Reproducibilidad de los ResultadosRESUMEN
An ecosystem services (ES) approach to chemical risk assessment has many potential advantages, but there are also substantial challenges regarding its implementation. We report the findings of a multi-stakeholder workshop that evaluated the feasibility of adopting an ES approach to chemical risk assessment using currently available tools and data. Also evaluated is the added value such an approach would bring to environmental decision making. The aim was to build consensus across disparate stakeholders and to co-produce a common understanding of the regulatory benefits and feasibility of implementing an ES approach in European chemicals regulation. Workshop discussions were informed by proof of concept studies and resulted in the development of a novel tiered framework for assessing chemical risk to ES delivery. There was consensus on the substantial added value of adopting an ES-based approach for regulatory decision making. Ecosystem services provide a common currency and a 'unifying approach' across environmental compartments, stressors and regulatory frameworks. The ES approach informs prioritisation of risk and remedial action and aids risk communication and risk management. It facilitates a more holistic assessment, enables ES trade-offs to be compared across alternative interventions, and supports comparative risk assessments and a socio-economic analysis of management options and decisions. Key to realising this added value is a shift away from using a single threshold value to categorise risk, towards a consideration of the exposure-effect distribution for individual ES of interest. Also required is the development of an integrated systems-level approach across regulatory frameworks and agreement on specific protection goals and scenarios for framing environmental risk assessments. The need to further develop tools for extrapolating toxicity data to service providers and ES delivery, including logic chains and ecological production functions, was highlighted. Also agreed was the need for methods and metrics for ES valuation to be used in assessing trade-offs.
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Conservación de los Recursos Naturales , Ecosistema , Medición de Riesgo , Gestión de RiesgosRESUMEN
The cyanoanthracene derivative, benzo[b]triphenylene-9,14-dicarbonitrile (1) can be prepared readily with a graftable function while maintaining (1)O(2) photosensitizing properties comparable to those of the standard compound 9,10-dicyanoanthracene (DCA). In view of the high potential of the derivatives of 1 for photooxidation reactions under heterogeneous conditions, we compared the photophysical properties of 1 in solution with those of DCA. In pursuing the comparison of 1 and DCA, we observed small but significant changes of the vibronic bands in the electronic absorption spectra of DCA in different solvents, which were well correlated with solvent polarity, similar to the pyrene polarity scale. The main difference between 1 and DCA is in the emission properties: we observed a much stronger sensitivity of the fluorescence emission spectrum to the electron-donating ability of the solvent than for DCA. The emission spectrum of 1 is in general structureless with a large Stokes shift. The ability of the singlet state of 1 to participate in charge transfer interactions with electron-donating solvents is proposed to account for these results. It makes 1 a highly sensitive probe to the surrounding medium. Reversible reduction was observed for both photosensitizers, with a small shift to more negative potentials for 1 compared to DCA. The reduction potential of the first singlet excited state is of the same order of magnitude in both cases. Several photo-oxidation reactions sensitized by 1 and DCA are compared in homogeneous solution and at the gas-solid interface by embedding 1 and DCA in silica monoliths. Our results confirmed the dual character of both cyanoanthracene derivatives as electron transfer and energy transfer sensitizers, highly efficient for singlet oxygen production.
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Molecular dynamics simulations are performed on the pure silica zeolite silicalite (MFI framework code), maintaining via a new force field both framework flexibility and realistic account of electrostatic interactions with adsorbed water. The force field is similar to the well-known "BKS" model [B. W. H. van Beest et al., Phys. Rev. Lett. 64, 1955 (1990)], but with reduced partial atomic charges and reoptimized covalent bond potential wells. The present force field reproduces the monoclinic to orthorhombic transition of silicalite. The force field correctly represents the hydrophobicity of pure silica silicalite, both the adsorption energy, and the molecular diffusion constants of water. Two types of adsorption, specific and weak unspecific, are predicted on the channel walls and at the channel intersection. We discuss molecular diffusion of water in silicalite, deducing a barrier to crossing between the straight and the zigzag channels. Analysis of the thermal motion shows that at room temperature, framework oxygen atoms incurring into the zeolite channels significantly influence the dynamics of adsorbed water.
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As COVID-19 spreads across the globe, a common public policy response has been to enforce the temporary closure of non-essential business activity. In some countries, governments have underwritten a proportion of the wage income for staff forced to furlough or broadened their welfare systems to accommodate newly laid off workers or small business owners. While these actions are helpful, they do not explicitly address the lack of sales trading activity on business income and cash balances. In commentary, we identify what types of businesses have been increasing their cash holdings in the lead up to COVID-19 as an indication of what types of small and medium-sized enterprises (SMEs) are most at risk if the lockdown extends for a protracted period of time. We find that only 39% of the of businesses were bolstering their cash balances leading up to COVID-19 which suggests that 61% of businesses may run out of cash, including 8.6% that had no retained earnings whatsoever with micro firms at particular risk. The importance of precautionary saving for SMEs is critical to enhance resilience when Black Swan events occur.