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1.
Nature ; 610(7932): 485-490, 2022 10.
Artigo em Inglês | MEDLINE | ID: mdl-36261554

RESUMO

Attitude control is an essential flight capability. Whereas flying robots commonly rely on accelerometers1 for estimating attitude, flying insects lack an unambiguous sense of gravity2,3. Despite the established role of several sense organs in attitude stabilization3-5, the dependence of flying insects on an internal gravity direction estimate remains unclear. Here we show how attitude can be extracted from optic flow when combined with a motion model that relates attitude to acceleration direction. Although there are conditions such as hover in which the attitude is unobservable, we prove that the ensuing control system is still stable, continuously moving into and out of these conditions. Flying robot experiments confirm that accommodating unobservability in this manner leads to stable, but slightly oscillatory, attitude control. Moreover, experiments with a bio-inspired flapping-wing robot show that residual, high-frequency attitude oscillations from flapping motion improve observability. The presented approach holds a promise for robotics, with accelerometer-less autopilots paving the road for insect-scale autonomous flying robots6. Finally, it forms a hypothesis on insect attitude estimation and control, with the potential to provide further insight into known biological phenomena5,7,8 and to generate new predictions such as reduced head and body attitude variance at higher flight speeds9.


Assuntos
Fenômenos Biomecânicos , Fluxo Óptico , Robótica , Animais , Voo Animal , Insetos , Modelos Biológicos , Robótica/métodos , Asas de Animais , Acelerometria , Biomimética , Materiais Biomiméticos , Movimento (Física)
2.
Inorg Chem ; 62(6): 2637-2651, 2023 Feb 13.
Artigo em Inglês | MEDLINE | ID: mdl-36716427

RESUMO

Desferrioxamine (DFO) has long been considered the gold standard chelator for incorporating [89Zr]Zr4+ in radiopharmaceuticals for positron emission tomography (PET) imaging. To improve the stability of DFO with zirconium-89 and to expand its coordination sphere to enable binding of large therapeutic radiometals, we have synthesized the highest denticity DFO derivatives to date: dodecadentate DFO2 and DFO2p. In this study, we describe the synthesis and characterization of a novel DFO-based chelator, DFO2p, which is comprised of two DFO strands connected by an p-NO2-phenyl linker and therefore contains double the chelating moieties of DFO (potential coordination number up to 12 vs 6). The chelator DFO2p offers an optimized synthesis comprised of only a single reaction step and improves water solubility relative to DFO2, but the shorter linker reduces molecular flexibility. Both DFO2 and DFO2p, each with 6 potential hydroxamate ligands, are able to reach a more energetically favorable 8-coordinate environment for Zr(IV) than DFO. The zirconium(IV) coordination environment of these complexes were evaluated by a combination of density functional theory (DFT) calculations and synchrotron spectroscopy (extended X-ray absorption fine structure), which suggest the inner-coordination sphere of zirconium(IV) to be comprised of the outermost four hydroxamate ligands. These results also confirm a single Zr(IV) in each chelator, and the hydroxide ligands which complete the coordination sphere of Zr(IV)-DFO are absent from Zr(IV)-DFO2 and Zr(IV)-DFO2p. Radiochemical stability studies with zirconium-89 revealed the order of real-world stability to be DFO2 > DFO2p ≫ DFO. The zirconium-89 complexes of these new high-denticity chelators were found to be far more stable than DFO, and the decreased molecular flexibility of DFO2p, relative to DFO2, could explain its decreased stability, relative to DFO2.

3.
J Phys Chem A ; 127(16): 3692-3704, 2023 Apr 27.
Artigo em Inglês | MEDLINE | ID: mdl-36912654

RESUMO

The sulfones are a widespread group of organo-sulfur compounds, which contain the sulfonyl SO2 group attached to two carbons and have a formal sulfur oxidation state of +2. We have examined the sulfur K near-edge X-ray absorption spectroscopy (XAS) of a range of different sulfones and find substantial spectroscopic variability depending upon the nature of the coordination to the sulfonyl group. We have also examined the sulfur Kß X-ray emission spectroscopy (XES) of selected representative sulfones. Density functional theory simulations show satisfactory reproduction of both absorption and emission spectra while enabling assignment of the various transitions comprising the spectra. The correspondence between observed and simulated spectra shows promise for ab initio prediction of sulfur X-ray absorption and emission spectra of sulfones of any substituent. The absorption spectra and, to a lesser extent, the emission spectra are sensitive to the nature of the organic groups bound to the sulfonyl (SO2) moiety, clearly showing the potential of X-ray spectroscopy as an in situ probe of sulfone chemistry.

4.
J Environ Manage ; 336: 117689, 2023 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-36924710

RESUMO

Multi-objective design approaches can help identify future infrastructure system designs that appropriately balance different engineering, environmental, and other societal goals. Planners benefit from assessing the trade-offs implied by the best-performing infrastructure system solutions. However, a large number of possible efficient system designs, obtained when using multi-objective optimization, can be overwhelming to interpret. This study attempts to aid decision-making in multi-criteria infrastructure system design by reducing the complexity of the identified set of efficient infrastructure designs, i.e., the Pareto-front. A soft clustering algorithm is applied, which identifies similarities between solutions, partitions the front accordingly, and selects a set of representative solutions while preserving the multi-dimensional structure of the solutions on the efficiency frontier. Three post-optimization decision-making metrics are introduced to help quantify the overall performance of the Pareto-optimal designs to further summarize design process outputs for decision-makers. We apply the method to an illustrious urban drainage network case study. Results show how the approach can simplify Pareto-fronts with thousands of solutions into sets of highlighted designs that aid interpreting the trade-offs implied by the best-performing simulated systems.


Assuntos
Algoritmos , Engenharia , Tomada de Decisões
5.
Inorg Chem ; 61(13): 5201-5214, 2022 Apr 04.
Artigo em Inglês | MEDLINE | ID: mdl-35073478

RESUMO

Mercury is in some sense an enigmatic element. The element and some of its compounds are a natural part of the biogeochemical cycle; while many of these can be deadly poisons at higher levels, environmental levels in the absence of anthropogenic contributions would generally be below the threshold for concern. However, mercury pollution, particularly from burning fossil fuels such as coal, is providing dramatic and increasing emissions into the environment. Because of this, the environmental chemistry and toxicology of mercury are of growing importance, with the fate of mercury being vitally dependent upon its speciation. X-ray absorption spectroscopy (XAS) provides a powerful tool for in situ chemical speciation, but is severely limited by poor spectroscopic energy resolution. Here, we provide a systematic examination of mercury Lα1 high energy resolution fluorescence detected XAS (HERFD-XAS) as an approach for chemical speciation of mercury, in quantitative comparison with conventional Hg LIII-edge XAS. We show that, unlike some lighter elements, chemical shifts in the Lα1 X-ray fluorescence energy can be safely neglected, so that mercury Lα1 HERFD-XAS can be treated simply as a high-resolution version of conventional XAS. We present spectra of a range of mercury compounds that may be relevant to the environmental and life science research and show that density functional theory can produce adequate simulations of the spectra. We discuss strengths and limitations of the method and quantitatively demonstrate improvements both in speciation for complex mixtures and in background rejection for low concentrations.


Assuntos
Mercúrio , Espectroscopia por Absorção de Raios X
6.
Fetal Diagn Ther ; 49(9-10): 377-384, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36044834

RESUMO

BACKGROUND: Given the maternal morbidity of open fetal surgery, the development of prenatal fetoscopic repair for spina bifida aperta (SBA) is encouraged. OBJECTIVE: We hereby report the early results from our center, using a laparotomy-assisted CO2-fetoscopic approach. METHODS: This study was conducted in patients with an SBA < T1 and >S1, <26 weeks of gestation, with Chiari II. Fetoscopic repair was performed using 2 operating trocars in the uterus exteriorized through a transverse laparotomy. Endoscopy was performed under humidified and heated CO2 insufflation. Following dissection of the lesion, a 1-layer approach was performed with a muscle/skin flap sutured over a patch of Duragen. Main outcomes were watertight repair at birth and the need for postnatal neurosurgical surgery including shunting within 6 months. RESULTS: Of 87 women assessed for prenatal therapy, 7 were included. Surgery was performed at 24 (23-26) weeks' gestation. There was no fetal demise. Conversion to hysterotomy was not performed, although surgery could not be performed in 1 case because of fetal position. Severe preeclampsia developed postoperatively in 1 case. In the other 6 cases, follow-up was uneventful except for premature rupture membranes which occurred in 3/6 cases at 30, 34, and 36+5 weeks' gestation. Gestational age at delivery was 32 + 5 (31-36 + 5) weeks' gestation. Repair was watertight at birth except in 2 cases which required complementary postnatal surgical repair. Reverse hindbrain herniation during pregnancy was observed in 4/6 cases. In 3/6 cases, shunting was necessary within 6 months after birth. At 12 months, a functional gain of ≥2 metameric levels was observed in 3 cases of the 6 survivors. CONCLUSION: Laparotomy-assisted fetoscopic repair is a reasonable option for women who choose and are eligible for antenatal surgery, both in terms of maternal and perinatal morbidity.


Assuntos
Meningomielocele , Espinha Bífida Cística , Recém-Nascido , Gravidez , Feminino , Humanos , Lactente , Espinha Bífida Cística/diagnóstico por imagem , Espinha Bífida Cística/cirurgia , Paris , Laparotomia , Dióxido de Carbono , Fetoscopia/métodos , Idade Gestacional , França , Meningomielocele/cirurgia
7.
J Environ Manage ; 302(Pt A): 114035, 2022 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-34741946

RESUMO

Climate change is a challenge to drinking water providers worldwide and to regulatory frameworks that consider long-term investment decisions. Coping with an unstable climate warrants adjustments in regulations and new investments. The investment required to maintain a selected service level needs to balance the potential for high regret stranded assets with the political and socioeconomic consequences of not meeting water demands. In recent years, the City of Santiago in Chile has seen drought events associated with climate change, which could worsen in the future. Chile's drinking water regulatory framework does not account for uncertainty in infrastructure design to cope with the potential impacts of such events. This work presents an adaptation option design process that considers multiple plausible climate change-impacted future scenarios, accommodating both structural and nonstructural measures. In our Santiago case study adaptation measures include extensions to the existing Chilean water market and traditional structural alternatives (e.g., storage infrastructure); all are represented in a simulation model of the water utility. We evaluate and optimize packages of efficient adaptation measures for various climate scenarios. This allows comparing different portfolios of combined institutional and infrastructure interventions via a range of stakeholder measures and comparing their tradeoffs under different plausible climate-impacted hydrological scenarios. Results showed that water supply performance without climate change adaptation is worse under climate scenarios with lower water availability, which are likely to be associated with higher GHG emission scenarios such as RCP 8.5. The optimized portfolios implement various combinations of adaptation strategies to reduce the impacts of this poor performance. Considering the uncertainty on future climate scenarios, the use of nonstructural adaptation measures such as option contracts exhibits the advantage of providing water in critical periods while avoiding large investments such as building reservoirs or the purchase of permanent water rights, which could end up underused if favorable climate scenarios manifest.


Assuntos
Mudança Climática , Água Potável , Chile , Secas , Abastecimento de Água
8.
Energy Econ ; 111: None, 2022 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-35781933

RESUMO

Large energy infrastructure can imply special financing arrangements between governments in developing economies and investors or lenders. These arrangements can lead to economy-wide and sector-specific impacts which need to be considered in the project economic evaluation. By considering the case of the Bui Dam in Ghana, we use a macroeconomic approach to determine how the economic performance of critical energy infrastructure manifests during the construction, financing and operation phases. The analysis uses an integrated modelling framework that combines a Computable General Equilibrium (CGE) model of Ghana with a water balance model of the Lower Volta River Basin. The results highlight the importance of including indirect and induced effects, in addition to the direct effects from project operation, as they influence the scale and temporal evolution of the economic impacts. The collateral from the infrastructure loan agreement consisting in cocoa exports to China nearly doubles the project's positive GDP impact and has a significant multiplier effect over urban and rural household income compared to a standard commercial loan. We finish with a discussion of how the proposed investment-oriented modelling framework can contribute to ex-ante strategic assessments of proposed energy infrastructure in developing countries.

9.
Anal Chem ; 93(26): 9235-9243, 2021 07 06.
Artigo em Inglês | MEDLINE | ID: mdl-34164981

RESUMO

Selenium is in many ways an enigmatic element. It is essential for health but toxic in excess, with the difference between the two doses being narrower than for any other element. Environmentally, selenium is of concern due to its toxicity. As the rarest of the essential elements, its low levels often provide challenges to the analytical chemist. X-ray absorption spectroscopy (XAS) provides a powerful tool for in situ chemical speciation but is severely limited by poor spectroscopic resolution arising from core-hole lifetime broadening. Here we explore selenium Kα1 high energy resolution fluorescence detected XAS (HERFD-XAS) as a novel approach for chemical speciation of selenium, in comparison with conventional Se K-edge XAS. We present spectra of a range of selenium species relevant to environmental and life science studies, including spectra of seleno-amino acids, which show strong similarities with S K-edge XAS of their sulfur congeners. We discuss strengths and limitations of HERFD-XAS, showing improvements in both speciation performance and low concentration detection. We also develop a simple method to correct fluorescence self-absorption artifacts, which is generally applicable to any HERFD-XAS experiment.


Assuntos
Selênio , Espectroscopia por Absorção de Raios X
10.
J Synchrotron Radiat ; 28(Pt 6): 1845-1849, 2021 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-34738938

RESUMO

Oxygen K-edge X-ray absorption spectroscopy is used routinely to study a range of solid materials. However, liquid samples are studied less frequently at the oxygen K-edge due to the combined challenges of high-vacuum conditions and oxygen contamination of window materials. A modular sample holder design with a twist-seal sample containment system that provides a simple method to encapsulate liquid samples under high-vacuum conditions is presented. This work shows that pure silicon nitride windows have lower oxygen contamination than both diamond- and silicon-rich nitride windows, that the levels of oxygen contamination are related to the age of the windows, and provides a protocol for minimizing the background oxygen contamination. Acid-washed 100 nm-thick silicon nitride windows were found to give good quality oxygen K-edge data on dilute liquid samples.


Assuntos
Oxigênio , Radiografia , Espectroscopia por Absorção de Raios X , Raios X
11.
Neuropathol Appl Neurobiol ; 47(1): 127-142, 2021 02.
Artigo em Inglês | MEDLINE | ID: mdl-32688444

RESUMO

AIMS: Histological analysis of brain tissue samples provides valuable information about the pathological processes leading to common neurodegenerative disorders. In this context, the development of novel high-resolution imaging approaches is a current challenge in neuroscience. METHODS: To this end, we used a recent super-resolution imaging technique called STochastic Optical Reconstruction Microscopy (STORM) to analyse human brain sections. We combined STORM cell imaging protocols with neuropathological techniques to image cryopreserved brain samples from control subjects and patients with neurodegenerative diseases. RESULTS: This approach allowed us to perform 2D-, 3D- and two-colour-STORM in neocortex, white matter and brainstem samples. STORM proved to be particularly effective at visualizing the organization of dense protein inclusions and we imaged with a <50 nm resolution pathological aggregates within the central nervous system of patients with Alzheimer's disease, Parkinson's disease, Lewy body dementia and fronto-temporal lobar degeneration. Aggregated Aß branches appeared reticulated and cross-linked in the extracellular matrix, with widths from 60 to 240 nm. Intraneuronal Tau and TDP-43 inclusions were denser, with a honeycomb pattern in the soma and a filamentous organization in the axons. Finally, STORM imaging of α-synuclein pathology revealed the internal organization of Lewy bodies that could not be observed by conventional fluorescence microscopy. CONCLUSIONS: STORM imaging of human brain samples opens further gates to a more comprehensive understanding of common neurological disorders. The convenience of this technique should open a straightforward extension of its application for super-resolution imaging of the human brain, with promising avenues to current challenges in neuroscience.


Assuntos
Doença de Alzheimer/patologia , Encéfalo/patologia , Microscopia , Doença de Parkinson/patologia , Humanos , Corpos de Inclusão/patologia , Corpos de Lewy/patologia , Doença por Corpos de Lewy/patologia , Masculino , Neurônios/patologia , alfa-Sinucleína/metabolismo , Proteínas tau/metabolismo
12.
Immunity ; 37(4): 649-59, 2012 Oct 19.
Artigo em Inglês | MEDLINE | ID: mdl-23063330

RESUMO

Type 2 innate lymphoid cells (ILC2s) are part of a large family of ILCs that are important effectors in innate immunity, lymphoid organogenesis, and tissue remodeling. ILC2s mediate parasite expulsion but also contribute to airway inflammation, emphasizing the functional similarity between these cells and Th2 cells. Consistent with this, we report that the transcription factor GATA3 was highly expressed by human ILC2s. CRTH2(+) ILC2s were enriched in nasal polyps of patients with chronic rhinosinusitis, a typical type 2-mediated disease. Nasal polyp epithelial cells expressed TSLP, which enhanced STAT5 activation, GATA3 expression, and type 2 cytokine production in ILC2s. Ectopic expression of GATA3 in Lin(-)CD127(+)CRTH2(-) cells resulted in induction of CRTH2 and the capacity to produce high amounts of type 2 cytokines in response to TSLP plus IL-33. Hence, we identify GATA3, potently regulated by TSLP, as an essential transcription factor for the function of human ILC2s.


Assuntos
Fator de Transcrição GATA3/imunologia , Imunidade Inata , Linfócitos/imunologia , Linhagem Celular , Citocinas/imunologia , Epitélio/imunologia , Regulação da Expressão Gênica , Humanos , Interleucina-13/biossíntese , Interleucina-13/imunologia , Pólipos Nasais/imunologia , Receptores de Citocinas/genética , Receptores de Citocinas/imunologia , Fator de Transcrição STAT5/imunologia , Linfopoietina do Estroma do Timo
13.
Phys Chem Chem Phys ; 23(8): 4500-4508, 2021 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-33355326

RESUMO

Until recently, sulfur was known as a "spectroscopically silent" element because of a paucity of convenient spectroscopic probes suitable for in situ chemical speciation. In recent years the technique of sulfur K-edge X-ray absorption spectroscopy (XAS) has been used extensively in sulfur speciation in a variety of different fields. With an initial focus on reduced forms of organic sulfur, we have explored a complementary X-ray based spectroscopy - sulfur Kß X-ray emission spectroscopy (XES) - as a potential analytical tool for sulfur speciation in complex samples. We compare and contrast the sensitivity of sulfur Kß XES with that of sulfur K-edge XAS, and find differing sensitivities for the two techniques. In some cases an approach involving both sulfur K-edge XAS and sulfur Kß XES may be a powerful combination for deducing sulfur speciation in samples containing complex mixtures.

14.
Eur J Immunol ; 49(2): 290-301, 2019 02.
Artigo em Inglês | MEDLINE | ID: mdl-30537036

RESUMO

Under homeostatic conditions, dendritic cells (DCs) continuously patrol the intestinal lamina propria. Upon antigen encounter, DCs initiate C-C motif chemokine receptor 7 (CCR7) expression and migrate into lymph nodes to direct T cell activation and differentiation. The mechanistic underpinnings of DC migration from the tissues to lymph nodes have been largely elucidated, contributing greatly to our understanding of DC functionality and intestinal immunity. In contrast, the molecular mechanisms allowing DCs to efficiently migrate through the complex extracellular matrix of the intestinal lamina propria prior to antigen encounter are still incompletely understood. Here we show that small intestinal murine CD11b+ CD103+ DCs express Placenta-expressed transcript 1 (Plet1), a glycophoshatidylinositol (GPI)-anchored surface protein involved in migration of keratinocytes during wound healing. In the absence of Plet1, CD11b+ CD103+ DCs display aberrant migratory behavior, and accumulate in the small intestine, independent of CCR7 responsiveness. RNA-sequencing indicated involvement of Plet1 in extracellular matrix-interactiveness, and subsequent in-vitro migration assays revealed that Plet1 augments the ability of DCs to migrate through extracellular matrix containing environments. In conclusion, our findings reveal that expression of Plet1 facilitates homeostatic interstitial migration of small intestinal DCs.


Assuntos
Movimento Celular/imunologia , Células Dendríticas/metabolismo , Regulação da Expressão Gênica/imunologia , Intestino Delgado/imunologia , Proteínas da Gravidez/imunologia , Animais , Antígenos CD/genética , Antígenos CD/imunologia , Movimento Celular/genética , Camundongos , Camundongos Knockout , Proteínas da Gravidez/genética
15.
Inorg Chem ; 59(23): 17443-17452, 2020 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-33183002

RESUMO

Positron emission tomography (PET) using radiolabeled, monoclonal antibodies has become an effective, noninvasive method for tumor detection and is a critical component of targeted radionuclide therapy. Metal ion chelator and bacterial siderophore desferrioxamine (DFO) is the gold standard compound for incorporation of zirconium-89 in radiotracers for PET imaging because it is thought to form a stable chelate with [89Zr]Zr4+. However, DFO may not bind zirconium-89 tightly in vivo, with free zirconium-89 reportedly liberated into the bones of experimental mouse models. Although high bone uptake has not been observed to date in humans, this potential instability has been proposed to be related to the unsaturated coordination sphere of [89Zr]Zr-DFO, which is thought to consist of the 3 hydroxamate groups of DFO and 1 or 2 water molecules. In this study, we have used a combination of X-ray absorption spectroscopy and density functional theory (DFT) geometry optimization calculations to further probe the coordination chemistry of this complex in solution. We find the extended X-ray absorption fine structure (EXAFS) curve fitting of an aqueous solution of Zr(IV)-DFO to be consistent with an 8-coordinate Zr with oxygen ligands. DFT calculations suggest that the most energetically favorable Zr(IV) coordination environment in DFO likely consists of the 3 hydroxamate ligands from DFO, each with bidentate coordination, and 2 hydroxide ligands. Further EXAFS curve fitting provides additional support for this model. Therefore, we propose that the coordination sphere of Zr(IV)-DFO is most likely completed by 2 hydroxide ligands rather than 2 water molecules, forming Zr(DFO)(OH)2.

16.
Environ Sci Technol ; 54(13): 7848-7857, 2020 07 07.
Artigo em Inglês | MEDLINE | ID: mdl-32525662

RESUMO

Urban concentrations of black carbon (BC) and other primary pollutants vary on small spatial scales (<100m). Mobile air pollution measurements can provide information on fine-scale spatial variation, thereby informing exposure assessment and mitigation efforts. However, the temporal sparsity of these measurements presents a challenge for estimating representative long-term concentrations. We evaluate the capabilities of mobile monitoring in the represention of time-stable spatial patterns by comparing against a large set of continuous fixed-site measurements from a sampling campaign in West Oakland, California. Custom-built, low-cost aerosol black carbon detectors (ABCDs) provided 100 days of continuous measurements at 97 near-road and 3 background fixed sites during summer 2017; two concurrently operated mobile laboratories collected over 300 h of in-motion measurements using a photoacoustic extinctiometer. The spatial coverage from mobile monitoring reveals patterns missed by the fixed-site network. Time-integrated measurements from mobile lab visits to fixed-site monitors reveal modest correlation (spatial R2 = 0.51) with medians of full daytime fixed-site measurements. Aggregation of mobile monitoring data in space and time can mitigate high levels of uncertainty associated with measurements at precise locations or points in time. However, concentrations estimated by mobile monitoring show a loss of spatial fidelity at spatial aggregations greater than 100 m.


Assuntos
Poluentes Atmosféricos , Poluição do Ar , Poluentes Atmosféricos/análise , Poluição do Ar/análise , Carbono , Monitoramento Ambiental , Material Particulado/análise , Fuligem/análise
17.
Fetal Diagn Ther ; 47(1): 74-83, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-31401627

RESUMO

BACKGROUND: In utero therapeutic approaches for lower urinary tract obstruction (LUTO) have been developed to salvage the fetal kidney function. OBJECTIVE: The aim of this work was to report the long-term survival, nephrological, and urological outcome of children treated prenatally for LUTO using operative fetal cystoscopy (FC) and vesicoamniotic shunting (VAS) or both. METHODS: A retrospective study of 48 procedures (23 FC, 25 VAS) was performed on 33 patients (between 2008 and 2018). Reviewed data included prenatal management and clinical follow-up by a pediatric nephrologist and a pediatric urologist. Both intention-to-treat and per-protocol analyses were conducted. RESULTS: The median follow-up was 3.6 years (0.5-7) for FC and 2.5 years (1.1-5.1) for VAS. There was no difference between FC and VAS in terms of survival (92 vs. 83%, p = 1), complication rate (74 vs. 92%, p = 0.88), or chronic kidney disease (58 vs. 50%, p = 1). The number of procedures was higher in the VAS group: 1.7 (1-3) versus 1.1 (1-2), p = 0.01. With a 30% rate of technical failure, FC added diagnostic value in 3 out of 21 cases. CONCLUSIONS: No difference was found between FC and VAS regarding survival, long-term kidney function, or urological outcome. Despite overly optimistic reports on FC, it lacks reproducibility due to posterior-urethra inadequate visualization and inappropriate instrumentation.


Assuntos
Cistoscopia/estatística & dados numéricos , Duodeno/anormalidades , Doenças Fetais/terapia , Terapias Fetais/estatística & dados numéricos , Sintomas do Trato Urinário Inferior/terapia , Bexiga Urinária/anormalidades , Feminino , Humanos , Gravidez , Estudos Retrospectivos , Resultado do Tratamento
18.
Environ Sci Technol ; 53(13): 7564-7573, 2019 07 02.
Artigo em Inglês | MEDLINE | ID: mdl-31244080

RESUMO

Ambient particulate matter (PM) pollution is a major environmental health risk in urban areas. Dense networks of low-cost air quality sensors are emerging to characterize the spatially heterogeneous concentrations that are typical of urban settings, but are not adequately captured using traditional regulatory monitors at central sites. In this study, we present the 100×100 BC Network, a 100-day deployment of low-cost black carbon (BC) sensors across 100 locations in West Oakland, California. This 15 km2 community is surrounded by freeways and affected by emissions associated with local port and industrial activities. We assess the reliability of the sensor hardware and data collection systems, and identify modes of failure to both quantify and qualify network performance. We illustrate how dynamic, local emission sources build upon background BC concentrations. BC concentrations varied sharply over short distances (∼100 m) and timespans (∼1 hour), depending on surrounding land use, traffic patterns, and downwind distance from pollution sources. Strong BC concentration fluctuations were periodically observed over the diurnal and weekly cycles, reflecting the impact of localized traffic emissions and industrial facilities in the neighborhood. Overall, the results demonstrate how distributed sensor networks can reveal the complex spatiotemporal dynamics of combustion-related air pollution within urban neighborhoods.


Assuntos
Poluentes Atmosféricos , Poluição do Ar , California , Carbono , Monitoramento Ambiental , Material Particulado , Reprodutibilidade dos Testes , Emissões de Veículos
19.
J Phys Chem A ; 123(13): 2861-2866, 2019 Apr 04.
Artigo em Inglês | MEDLINE | ID: mdl-30836751

RESUMO

Aryl and mixed aryl-alkyl organic sulfides are important species in a variety of fields, including the drug and food industries. They also are present in fossil fuels, where they contribute to the range of sulfur compounds that must be removed by the fuel industry. We have used sulfur K-edge X-ray absorption spectroscopy, in combination with density functional theory calculations, to study the aryl sulfide diphenyl sulfide and two different aryl-alkyl sulfides. The sulfur K near-edge X-ray absorption spectra are strongly affected by the coordination of the phenyl ring and are distinct from spectra of the alkyl sulfides. For diphenyl sulfide the spectra are predicted to be sensitive to rotation about the S-C bonds, with experimental spectra corresponding to a sum of thermally accessible conformations. We also have investigated the vapor-phase spectrum of diphenyl sulfide, which is found to be very similar to that of toluene solutions of the compound.

20.
Inorg Chem ; 57(14): 8205-8210, 2018 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-29956922

RESUMO

We use X-ray-induced photochemistry, which is well known to cause changes in a number of systems, to reduce Hg(II) to Hg(0) in frozen aqueous solution with added glycerol maintained at 10 K. X-ray absorption spectroscopy was used to monitor the extent of the reaction and to characterize the species. An analysis of the extended X-ray absorption fine structure (EXAFS) of the photochemical product indicated a nearly monatomic Hg(0) species bound only by long, weak bonds to oxygens at ∼3.5 Å. The results of the EXAFS analysis agree quantitatively with the results of density functional theory calculations using the meta-GGA approximation with the M11-L functional. This is the first structural characterization of nearly monatomic Hg(0) bound by hard ligands similar to those expected in aqueous environmental systems. We conclude that Hg(0) is expected to exist in solution as a nearly monatomic entity.

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