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1.
Am J Bot ; 111(2): e16276, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38297448

RESUMO

PREMISE: Dioecy (separate sexes) has independently evolved numerous times across the angiosperm phylogeny and is recently derived in many lineages. However, our understanding is limited regarding the evolutionary mechanisms that drive the origins of dioecy in plants. The recent and repeated evolution of dioecy across angiosperms offers an opportunity to make strong inferences about the ecological, developmental, and molecular factors influencing the evolution of dioecy, and thus sex chromosomes. The genus Asparagus (Asparagaceae) is an emerging model taxon for studying dioecy and sex chromosome evolution, yet estimates for the age and origin of dioecy in the genus are lacking. METHODS: We use plastome sequences and fossil time calibrations in phylogenetic analyses to investigate the age and origin of dioecy in the genus Asparagus. We also review the diversity of sexual systems present across the genus to address contradicting reports in the literature. RESULTS: We estimate that dioecy evolved once or twice approximately 2.78-3.78 million years ago in Asparagus, of which roughly 27% of the species are dioecious and the remaining are hermaphroditic with monoclinous flowers. CONCLUSIONS: Our findings support previous work implicating a young age and the possibility of two origins of dioecy in Asparagus, which appear to be associated with rapid radiations and range expansion out of Africa. Lastly, we speculate that paleoclimatic oscillations throughout northern Africa may have helped set the stage for the origin(s) of dioecy in Asparagus approximately 2.78-3.78 million years ago.


Assuntos
Evolução Biológica , Cromossomos Sexuais , Filogenia , África , África do Norte
2.
Philos Trans A Math Phys Eng Sci ; 378(2183): 20190314, 2020 Oct 30.
Artigo em Inglês | MEDLINE | ID: mdl-32981430

RESUMO

Air pollution has been recognized as a threat to human health since the time of Hippocrates, ca 400 BC. Successive written accounts of air pollution occur in different countries through the following two millennia until measurements, from the eighteenth century onwards, show the growing scale of poor air quality in urban centres and close to industry, and the chemical characteristics of the gases and particulate matter. The industrial revolution accelerated both the magnitude of emissions of the primary pollutants and the geographical spread of contributing countries as highly polluted cities became the defining issue, culminating with the great smog of London in 1952. Europe and North America dominated emissions and suffered the majority of adverse effects until the latter decades of the twentieth century, by which time the transboundary issues of acid rain, forest decline and ground-level ozone became the main environmental and political air quality issues. As controls on emissions of sulfur and nitrogen oxides (SO2 and NOx) began to take effect in Europe and North America, emissions in East and South Asia grew strongly and dominated global emissions by the early years of the twenty-first century. The effects of air quality on human health had also returned to the top of the priorities by 2000 as new epidemiological evidence emerged. By this time, extensive networks of surface measurements and satellite remote sensing provided global measurements of both primary and secondary pollutants. Global emissions of SO2 and NOx peaked, respectively, in ca 1990 and 2018 and have since declined to 2020 as a result of widespread emission controls. By contrast, with a lack of actions to abate ammonia, global emissions have continued to grow. This article is part of a discussion meeting issue 'Air quality, past present and future'.


Assuntos
Poluição do Ar , Chuva Ácida , Poluentes Atmosféricos/análise , Poluição do Ar/efeitos adversos , Poluição do Ar/história , Poluição do Ar/legislação & jurisprudência , Cidades , Ecossistema , Monitoramento Ambiental , Eutrofização , Saúde Global/história , História do Século XVII , História do Século XVIII , História do Século XIX , História do Século XX , História do Século XXI , História Antiga , História Medieval , Humanos , Ozônio/análise , Material Particulado/análise , Tecnologia de Sensoriamento Remoto
3.
J Quant Spectrosc Radiat Transf ; 256: 107270, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32868955

RESUMO

After several decades' development of retrieval techniques in aerosol remote sensing, no fast and accurate analytical Radiative Transfer Model (RTM) has been developed and applied to create global aerosol products for non-polarimetric instruments such as Ocean and Land Colour Instrument/Sentinel-3 (OLCI/Sentinel-3) and Meteosat Second Generation/Spinning Enhanced Visible and Infrared Imager (MSG/SEVIRI). Global aerosol retrieval algorithms are typically based on a Look-Up-Table (LUT) technique, requiring high-performance computers. The current eXtensible Bremen Aerosol/cloud and surfacE parameters Retrieval (XBAER) algorithm also utilizes the LUT method. In order to have a near-real time retrieval and achieve a quick and accurate "FIRST-LOOK" aerosol product without high-demand of computing resource, we have developed a Fast and Accurate Semi-analytical Model of Atmosphere-surface Reflectance (FASMAR) for aerosol remote sensing. The FASMAR is developed based on a successive order of scattering technique. In FASMAR, the first three orders of scattering are calculated exactly. The contribution of higher orders of scattering is estimated using an extrapolation technique and an additional correction function. The evaluation of FASMAR has been performed by comparing with radiative transfer model SCIATRAN for all typical observation/illumination geometries, surface/aerosol conditions, and wavelengths 412, 550, 670, 870, 1600, 2100 nm used for aerosol remote sensing. The selected observation/illumination conditions are based on the observations from both geostationary satellite (e.g. MSG/SEVIRI) and polar-orbit satellite (e.g. OLCI/Sentinel-3). The percentage error of the top of atmosphere reflectance calculated by FASMAR is within  ± 3% for typical polar-orbit/geostationary satellites' observation/illumination geometries. The accuracy decreases for solar and viewing zenith angles larger than 70∘. However, even in such cases, the error is within the range  ± 5%. The evaluation of model performance also shows that FASMAR can be used for all typical surfaces with albedo in the interval [ 0 - 1 ] and aerosol with optical thickness in the range [ 0.01 - 1 ] .

4.
Opt Express ; 27(12): A829-A855, 2019 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-31252858

RESUMO

Underwater light field characterization is of importance for understanding biogeochemical processes and heat budget of the global oceans, which are impacting and reacting to climate change. Vibrational Raman Scattering (VRS) was retrieved from backscattered radiances measured by three different hyperspectral satellite sensors, SCIAMACHY, GOME-2, and OMI, using Differential Optical Absorption Spectroscopy (DOAS). Diffuse attenuation coefficient (Kd) in the blue spectral range (390 to 426 nm) was derived from the VRS signal via a look-up-table established through ocean-atmosphere coupled radiative transfer modeling. We processed one year of data, representative of the overlapping period of optimal operation for all three sensors. Resulting data sets were evaluated by comparison with Kd at 490 nm from Ocean Colour Climate Change Initiative (OC-CCI) which was first converted to Kd at 390 to 426 nm. Good agreement with the OC-CCI Kd product was achieved for all three sensors when Kd was limited to below 0.15 m-1. Differences among the hyperspectral sensors and to OC-CCI were attributed to particular instrumental effects on the DOAS retrieval leading to temporal and spatial biases. This is in addition to the fact that the spatial and temporal resolution of the hyperspectral sensors data differ among themselves and are much lower then for the OC-CCI Kd-product. Further corrections (e.g., empirical) are necessary before these data sets can be merged in order to obtain a long-term Kd product for the blue spectral range.

5.
J Environ Sci (China) ; 71: 108-118, 2018 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-30195669

RESUMO

Currently, modeling studies tend to significantly underestimate observed space-based glyoxal (CHOCHO) vertical column densities (VCDs), implying the existence of missing sources of glyoxal. Several recent studies suggest that the emissions of aromatic compounds and molar yields of glyoxal in the chemical mechanisms may both be underestimated, which can affect the simulated glyoxal concentrations. In this study, the influences of these two factors on glyoxal amounts over China were investigated using the RAMS-CMAQ modeling system for January and July 2014. Four sensitivity simulations were performed, and the results were compared to satellite observations. These results demonstrated significant impacts on glyoxal concentrations from these two factors. In case 1, where the emissions of aromatic compounds were increased three-fold, improvements to glyoxal VCDs were seen in high anthropogenic emissions regions. In case 2, where molar yields of glyoxal from isoprene were increased five-fold, the resulted concentrations in July were 3-5-fold higher, achieving closer agreement between the modeled and measured glyoxal VCDs. The combined changes from both cases 1 and 2 were applied in case 3, and the model succeeded in further reducing the underestimations of glyoxal VCDs. However, the results over most of the regions with pronounced anthropogenic emissions were still underestimated. So the molar yields of glyoxal from anthropogenic precursors were considered in case 4. With these additional mole yield changes (a two-fold increase), the improved concentrations agreed better with the measurements in regions of the lower reaches of the Yangtze River and Yellow River in January but not in July.


Assuntos
Poluentes Atmosféricos/análise , Poluição do Ar/estatística & dados numéricos , Monitoramento Ambiental/métodos , Glioxal/análise , Modelos Químicos
6.
Remote Sens Environ ; 197: 125-140, 2017 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-29760534

RESUMO

The MEdium Resolution Imaging Spectrometer (MERIS) instrument on board ESA Envisat made measurements from 2002 to 2012. Although MERIS was limited in spectral coverage, accurate Aerosol Optical Thickness (AOT) from MERIS data are retrieved by using appropriate additional information. We introduce a new AOT retrieval algorithm for MERIS over land surfaces, referred to as eXtensible Bremen AErosol Retrieval (XBAER). XBAER is similar to the "dark-target" (DT) retrieval algorithm used for Moderate-resolution Imaging Spectroradiometer (MODIS), in that it uses a lookup table (LUT) to match to satellite-observed reflectance and derive the AOT. Instead of a global parameterization of surface spectral reflectance, XBAER uses a set of spectral coefficients to prescribe surface properties. In this manner, XBAER is not limited to dark surfaces (vegetation) and retrieves AOT over bright surface (desert, semiarid, and urban areas). Preliminary validation of the MERIS-derived AOT and the ground-based Aerosol Robotic Network (AERONET) measurements yield good agreement, the resulting regression equation is y = (0.92 × ± 0.07) + (0.05 ± 0.01) and Pearson correlation coefficient of R = 0.78. Global monthly means of AOT have been compared from XBAER, MODIS and other satellite-derived datasets.

8.
Med Law Rev ; 24(2): 278-85, 2016.
Artigo em Inglês | MEDLINE | ID: mdl-26856615

RESUMO

The Ronayne case concerned a husband who suffered a psychiatric illness, described as an adjustment disorder, in seeing the condition of his wife who was the primary victim of admitted medical negligence. His claim for compensation, as a 'secondary victim', failed because he could not satisfy the legal requirement that there must be a sudden shocking event. This commentary criticises that requirement which appears to make no medical sense.


Assuntos
Compensação e Reparação , Responsabilidade Legal , Imperícia , Transtornos Mentais , Feminino , Humanos , Masculino , Medicina Estatal , Reino Unido
9.
New Phytol ; 204(1): 201-214, 2014 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-25039765

RESUMO

The origin of fire-adapted lineages is a long-standing question in ecology. Although phylogeny can provide a significant contribution to the ongoing debate, its use has been precluded by the lack of comprehensive DNA data. Here, we focus on the 'underground trees' (=geoxyles) of southern Africa, one of the most distinctive growth forms characteristic of fire-prone savannas. We placed geoxyles within the most comprehensive dated phylogeny for the regional flora comprising over 1400 woody species. Using this phylogeny, we tested whether African geoxyles evolved concomitantly with those of the South American cerrado and used their phylogenetic position to date the appearance of humid savannas. We found multiple independent origins of the geoxyle life-form mostly from the Pliocene, a period consistent with the origin of cerrado, with the majority of divergences occurring within the last 2 million yr. When contrasted with their tree relatives, geoxyles occur in regions characterized by higher rainfall and greater fire frequency. Our results indicate that the geoxylic growth form may have evolved in response to the interactive effects of frequent fires and high precipitation. As such, geoxyles may be regarded as markers of fire-maintained savannas occurring in climates suitable for forests.


Assuntos
Incêndios , Florestas , Pradaria , Adaptação Biológica , África , Biodiversidade , Evolução Biológica , Brasil , Ecossistema , Filogenia
10.
J Am Heart Assoc ; 13(9): e033253, 2024 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-38686864

RESUMO

BACKGROUND: The digital transformation of medical data enables health systems to leverage real-world data from electronic health records to gain actionable insights for improving hypertension care. METHODS AND RESULTS: We performed a serial cross-sectional analysis of outpatients of a large regional health system from 2010 to 2021. Hypertension was defined by systolic blood pressure ≥140 mm Hg, diastolic blood pressure ≥90 mm Hg, or recorded treatment with antihypertension medications. We evaluated 4 methods of using blood pressure measurements in the electronic health record to define hypertension. The primary outcomes were age-adjusted prevalence rates and age-adjusted control rates. Hypertension prevalence varied depending on the definition used, ranging from 36.5% to 50.9% initially and increasing over time by ≈5%, regardless of the definition used. Control rates ranged from 61.2% to 71.3% initially, increased during 2018 to 2019, and decreased during 2020 to 2021. The proportion of patients with a hypertension diagnosis ranged from 45.5% to 60.2% initially and improved during the study period. Non-Hispanic Black patients represented 25% of our regional population and consistently had higher prevalence rates, higher mean systolic and diastolic blood pressure, and lower control rates compared with other racial and ethnic groups. CONCLUSIONS: In a large regional health system, we leveraged the electronic health record to provide real-world insights. The findings largely reflected national trends but showed distinctive regional demographics and findings, with prevalence increasing, one-quarter of the patients not controlled, and marked disparities. This approach could be emulated by regional health systems seeking to improve hypertension care.


Assuntos
Registros Eletrônicos de Saúde , Hipertensão , Humanos , Hipertensão/epidemiologia , Hipertensão/tratamento farmacológico , Hipertensão/diagnóstico , Masculino , Feminino , Pessoa de Meia-Idade , Estudos Transversais , Prevalência , Idoso , Pressão Sanguínea/efeitos dos fármacos , Adulto , Disparidades em Assistência à Saúde/tendências , Fatores de Tempo , Anti-Hipertensivos/uso terapêutico , Disparidades nos Níveis de Saúde , Determinação da Pressão Arterial/métodos
11.
PhytoKeys ; 189: 61-80, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35136361

RESUMO

An updated checklist of Mozambique's vascular plants is presented. It was compiled referring to several information sources such as existing literature, relevant online databases and herbaria collections. The checklist includes 7,099 taxa (5,957 species, 605 subspecies, 537 varieties), belonging to 226 families and 1,746 genera. There are 6,804 angiosperms, 257 pteridophytes, and 38 gymnosperms. A total of 6,171 taxa are native to Mozambique, while 602 are introduced and the remaining 326 taxa were considered as uncertain status. The endemism level for Mozambique's flora was assessed at 9.59%, including 278 strict-endemic taxa and 403 near-endemic. 58.2% of taxa are herbaceous, while shrubs and trees account respectively for 26.5% and 9.2% of the taxa. The checklist also includes ferns (3.6%), lianas (1.7%), subshrubs (0.5%) and cycads (0.3%). Fabaceae, Poaceae and Asteraceae are the three most represented families, with 891, 543 and 428 taxa, respectively. The extinction risk of 1,667 taxa is included, with 158 taxa listed as Vulnerable, 119 as Endangered and as 24 Critically Endangered. The geographical distribution, known vernacular names and plants traditional uses are also recorded.

12.
Nature ; 437(7055): 129-32, 2005 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-16136141

RESUMO

Emissions from fossil fuel combustion and biomass burning reduce local air quality and affect global tropospheric chemistry. Nitrogen oxides are emitted by all combustion processes and play a key part in the photochemically induced catalytic production of ozone, which results in summer smog and has increased levels of tropospheric ozone globally. Release of nitrogen oxide also results in nitric acid deposition, and--at least locally--increases radiative forcing effects due to the absorption of downward propagating visible light. Nitrogen oxide concentrations in many industrialized countries are expected to decrease, but rapid economic development has the potential to increase significantly the emissions of nitrogen oxides in parts of Asia. Here we present the tropospheric column amounts of nitrogen dioxide retrieved from two satellite instruments GOME and SCIAMACHY over the years 1996-2004. We find substantial reductions in nitrogen dioxide concentrations over some areas of Europe and the USA, but a highly significant increase of about 50 per cent-with an accelerating trend in annual growth rate-over the industrial areas of China, more than recent bottom-up inventories suggest.


Assuntos
Poluição do Ar/análise , Atmosfera/química , Dióxido de Nitrogênio/análise , Comunicações Via Satélite , Poluentes Atmosféricos/análise , Poluentes Atmosféricos/provisão & distribuição , Poluição do Ar/estatística & dados numéricos , Biomassa , China , Europa (Continente) , Combustíveis Fósseis/estatística & dados numéricos , Modelos Lineares , Dióxido de Nitrogênio/química , América do Norte , Ozônio/análise , Fatores de Tempo
13.
J Glob Health ; 9(1): 010407, 2019 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-30603078

RESUMO

BACKGROUND: Clostridium difficile is a leading cause of morbidity and mortality in several countries. However, there are limited evidence characterizing its role as a global public health problem. We conducted a systematic review to provide a comprehensive overview of C. difficile infections (CDI) rates. METHODS: Seven databases were searched (January 2016) to identify studies and surveillance reports published between 2005 and 2015 reporting CDI incidence rates. CDI incidence rates for health care facility-associated (HCF), hospital onset-health care facility-associated, medical or general intensive care unit (ICU), internal medicine (IM), long-term care facility (LTCF), and community-associated (CA) were extracted and standardized. Meta-analysis was conducted using a random effects model. RESULTS: 229 publications, with data from 41 countries, were included. The overall rate of HCF-CDI was 2.24 (95% confidence interval CI = 1.66-3.03) per 1000 admissions/y and 3.54 (95%CI = 3.19-3.92) per 10 000 patient-days/y. Estimated rates for CDI with onset in ICU or IM wards were 11.08 (95%CI = 7.19-17.08) and 10.80 (95%CI = 3.15-37.06) per 1000 admission/y, respectively. Rates for CA-CDI were lower: 0.55 (95%CI = 0.13-2.37) per 1000 admissions/y. CDI rates were generally higher in North America and among the elderly but similar rates were identified in other regions and age groups. CONCLUSIONS: Our review highlights the widespread burden of disease of C. difficile, evidence gaps, and the need for sustainable surveillance of CDI in the health care setting and the community.


Assuntos
Infecções por Clostridium/epidemiologia , Saúde Global/estatística & dados numéricos , Humanos , Incidência
14.
Lancet Glob Health ; 7(1): e47-e57, 2019 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-30497986

RESUMO

BACKGROUND: Global child mortality reduced substantially during the Millennium Development Goal period (2000-15). We aimed to estimate morbidity, mortality, and prevalence of risk factors for child pneumonia at the global, regional, and national level for developing countries for the Millennium Development Goal period. METHODS: We estimated the incidence, number of hospital admissions, and in-hospital mortality due to all-cause clinical pneumonia in children younger than 5 years in developing countries at 5-year intervals during the Millennium Development Goal period (2000-15) using data from a systematic review and Poisson regression. We estimated the incidence and number of cases of clinical pneumonia, and the pneumonia burden attributable to HIV for 132 developing countries using a risk-factor-based model that used Demographic and Health Survey data on prevalence of the various risk factors for child pneumonia. We also estimated pneumonia mortality in young children using data from multicause models based on vital registration and verbal autopsy. FINDINGS: Globally, the number of episodes of clinical pneumonia in young children decreased by 22% from 178 million (95% uncertainty interval [UI] 110-289) in 2000 to 138 million (86-226) in 2015. In 2015, India, Nigeria, Indonesia, Pakistan, and China contributed to more than 54% of all global pneumonia cases, with 32% of the global burden from India alone. Between 2000 and 2015, the burden of clinical pneumonia attributable to HIV decreased by 45%. Between 2000 and 2015, global hospital admissions for child pneumonia increased by 2·9 times with a more rapid increase observed in the WHO South-East Asia Region than the African Region. Pneumonia deaths in this age group decreased from 1·7 million (95% UI 1·7-2·0) in 2000 to 0·9 million (0·8-1·1) in 2015. In 2015, 49% of global pneumonia deaths occurred in India, Nigeria, Pakistan, Democratic Republic of the Congo, and Ethiopia collectively. All key risk factors for child pneumonia (non-exclusive breastfeeding, crowding, malnutrition, indoor air pollution, incomplete immunisation, and paediatric HIV), with the exception of low birthweight, decreased across all regions between 2000 and 2015. INTERPRETATION: Globally, the incidence of child pneumonia decreased by 30% and mortality decreased by 51% during the Millennium Development Goal period. These reductions are consistent with the decrease in the prevalence of some of the key risk factors for pneumonia, increasing socioeconomic development and preventive interventions, improved access to care, and quality of care in hospitals. However, intersectoral action is required to improve socioeconomic conditions and increase coverage of interventions targeting risk factors for child pneumonia to accelerate decline in pneumonia mortality and achieve the Sustainable Development Goals for health by 2030. FUNDING: Bill & Melinda Gates Foundation.


Assuntos
Mortalidade da Criança/tendências , Saúde Global/estatística & dados numéricos , Pneumonia/epidemiologia , Pré-Escolar , Humanos , Lactente , Pneumonia/mortalidade
15.
Environ Pollut ; 252(Pt A): 256-269, 2019 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-31153030

RESUMO

We investigate the distribution of volatile organic compounds (VOCs) over Indian subcontinent during a winter month of January 2011 combining the regional model WRF-Chem (Weather Research and Forecasting model coupled with Chemistry) with ground- and space-based observations and chemical reanalysis. WRF-Chem simulated VOCs are found to be comparable with ground-based observations over contrasting environments of the Indian subcontinent. WRF-Chem results reveal the elevated levels of VOCs (e. g. propane) over the Indo-Gangetic Plain (16 ppbv), followed by the Northeast region (9.1 ppbv) in comparison with other parts of the Indian subcontinent (1.3-8.2 ppbv). Higher relative abundances of propane (27-31%) and ethane (13-17%) are simulated across the Indian subcontinent. WRF-Chem simulated formaldehyde and glyoxal show the western coast, Eastern India and the Indo-Gangetic Plain as the regional hotspots, in a qualitative agreement with the MACC (Monitoring Atmospheric Composition and Climate) reanalysis and satellite-based observations. Lower values of RGF (ratio of glyoxal to formaldehyde <0.04) suggest dominant influences of the anthropogenic emissions on the distribution of VOCs over Indian subcontinent, except the northeastern region where higher RGF (∼0.06) indicates the role of biogenic emissions, in addition to anthropogenic emissions. Analysis of HCHO/NO2 ratio shows a NOx-limited ozone production over India, with a NOx-to-VOC transition regime over central India and IGP. The study highlights a need to initiate in situ observations of VOCs over regional hotspots (Northeast, Central India, and the western coast) based on WRF-Chem results, where different satellite-based observations differ significantly.


Assuntos
Poluentes Atmosféricos/análise , Simulação por Computador , Monitoramento Ambiental/métodos , Ozônio/análise , Imagens de Satélites , Compostos Orgânicos Voláteis/análise , Clima , Etano/análise , Previsões , Formaldeído/análise , Glioxal/análise , Índia , Propano/análise , Estações do Ano , Tempo (Meteorologia)
16.
Artigo em Inglês | MEDLINE | ID: mdl-16387540

RESUMO

Optical multichannel detectors like photodiode arrays or CCD cameras combined with grating spectrometers are commonly used as detection systems in quantitative absorption spectroscopy. As a trade-off to broad spectral coverage, banded spectral features are sometimes recorded with insufficient spectral resolution and/or insufficiently fine detector binning. This renders the true physical spectrum of recorded intensities changed by instrumental and spectrum specific artefacts thus impeding comparability between results from different set-ups. In this work, it is demonstrated that in the case of a "well-behaved"--i.e. free of ro-vibronic structure--absorption band like the iodine monoxide IO(4<--0) transition, these effects can easily change the apparent peak absorption by up to 50%. Also deviations from the strict linearity (Beer-Lambert's law) between absorber concentration and apparent, i.e. pixelwise optical density occur. This can be critical in studies of chemical kinetics. It is shown that the observed non-linearity can cause errors of up to 50% in the determination of a second order rate coefficient for the IO self reaction. To overcome the problem, a consistent and rigorous integral approach for the treatment of intensity recordings is developed. Linearity between optical density and absorber concentration thereby is re-established. The method is validated using artificial test data as well as experimental data of the IO(4<--0) absorption transition, obtained in the context of I2/O3 photochemistry studies. The agreement is accurate to within +/-2% (test data) and +/-3% (experimental data) supporting the validity of the approach. Possible consequences for other spectroscopic work are indicated.


Assuntos
Compostos de Iodo/química , Dinâmica não Linear , Cinética , Análise Espectral
17.
Bioanalysis ; 7(14): 1731-43, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-26270781

RESUMO

Traditional approaches to the assessment of the linearity of chromatographic assays initially assume that the concentration-response relationship is linear and only deemed to be nonlinear if certain parameters lie outside pre-set acceptance criteria. A different approach is described in that the a priori assumption is made that the assay does have some curvature that can be described by fitting a nonlinear regression curve. Any nonlinearity can be quantified from the curvature terms of the resultant regression coefficients. The success of this alternative approach is dependent upon the appropriate choice of nonlinear regression to accurately describe concentration versus response relationship of the assay.


Assuntos
Cromatografia/métodos , Dinâmica não Linear
18.
Bioanalysis ; 7(14): 1745-61, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-26270782

RESUMO

In Part I of this series of communications an alternative approach was outlined to quantify the deviation from linearity by estimation of the change in true sensitivity of several mathematically defined concentration-response relationships. In this paper, Monte Carlo techniques were used to compare the strengths and limitations of linear and nonlinear regressions in assay calibrations. Nonlinear regressions can define a calibration curve as efficiently as a linear regression. Provided that the nonlinear regression is matched to the actual nonlinear concentration-response relationship, the use of nonlinear regressions can improve the accuracy of the assay and increase the percentage of calibrations meeting acceptance criteria.


Assuntos
Cromatografia/métodos , Dinâmica não Linear
19.
Bioanalysis ; 7(14): 1763-74, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-26270783

RESUMO

Chromatography-based drug assays are generally considered to be linear, provided that the back calculated concentrations of 75% of the calibrators are within ±15% of their target values. Data meeting this criterion are not usually subject to further examination in order to evaluate the extent of any nonlinearity and whether use of a nonlinear calibration function would improve the accuracy. Examples of nonlinear behavior are presented for several chromatographic systems and most are best described by the nonlinear equation y = a + bx + cxln(x). A more critical evaluation of linearity, as presented herein, can lead to the identification of nonlinear behavior and an improvement in accuracy by use of a nonlinear calibration regression.


Assuntos
Cromatografia/métodos , Dinâmica não Linear
20.
Spectrochim Acta A Mol Biomol Spectrosc ; 60(11): 2673-93, 2004 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-15294259

RESUMO

The separation of overlapping absorption spectra in the context of multichannel time-resolved absorption spectroscopy and chemical kinetics is a particular case in the general problem of splitting the observed data into several linear components. Here, principal and independent components analysis are applied to kinetic data of iodine--ozone chemistry, which contains overlapping spectra of different absorbers. The objective of this work is to demonstrate a method which in spite of this overlap is able to extract separated time traces of such absorbers. These time traces are clearly a pre-requisite for any further accurate quantitative analysis. The statistical properties of data recordings obtained from flash photolysis of I(2) and O(3) have been studied to check if the requirements of the model are fulfilled. Results of separation in appropriate spectral windows displaying overlapped vibrational features are presented. Validation is made using prior information and conventional techniques.


Assuntos
Técnicas de Química Analítica , Iodo/química , Ozônio/química , Cinética , Modelos Químicos , Análise de Componente Principal , Análise Espectral , Fatores de Tempo
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