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1.
Integr Comp Biol ; 2024 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-38641425

RESUMO

Emerging mycoses are an increasing concern in wildlife and human health. Given the historical rarity of fungal pathogens in warm-bodied vertebrates, there is a need to better understand how to manage mycoses and facilitate recovery in affected host populations. We explore challenges to host survival and mechanisms of host recovery in three bat species (Myotis lucifugus, Perimyotis subflavus, and M. septentrionalis) threatened with extinction by the mycosis, White-nose Syndrome (WNS) as it continues to spread across North America. We present evidence from the literature that bats surviving WNS are exhibiting mechanisms of avoidance (by selecting microclimates within roosts) and tolerance (by increasing winter fat reserves), which may help avoid costs of immunopathology incurred by a maladaptive host resistance response. We discuss management actions for facilitating species recovery that take into consideration disease pressures (e.g., environmental reservoir) and mechanisms underlying persistence, and suggest strategies that alleviate costs of immunopathology and target mechanisms of avoidance (protect or create refugia) and tolerance (increase body condition). We also propose strategies that target population and species-level recovery, including increasing reproductive success and reducing other stressors (e.g., wind turbine mortality). The rarity of fungal pathogens paired with the increasing frequency of emerging mycoses in warm-bodied vertebrate systems, including humans, requires a need to challenge common conventions about how diseases operate, how hosts respond, and how these systems could be managed to increase probability of recovery in host populations.

2.
Sci Adv ; 6(19): eaat9488, 2020 May.
Artigo em Inglês | MEDLINE | ID: mdl-32494692

RESUMO

The existence of nontrivial Berry phases associated with two inequivalent valleys in graphene provides interesting opportunities for investigating the valley-projected topological states. Examples of such studies include observation of anomalous quantum Hall effect in monolayer graphene, demonstration of topological zero modes in "molecular graphene" assembled by scanning tunneling microscopy, and detection of topological valley transport either in graphene superlattices or at bilayer graphene domain walls. However, all aforementioned experiments involved nonscalable approaches of either mechanically exfoliated flakes or atom-by-atom constructions. Here, we report an approach to manipulating the topological states in monolayer graphene via nanoscale strain engineering at room temperature. By placing strain-free monolayer graphene on architected nanostructures to induce global inversion symmetry breaking, we demonstrate the development of giant pseudo-magnetic fields (up to ~800 T), valley polarization, and periodic one-dimensional topological channels for protected propagation of chiral modes in strained graphene, thus paving a pathway toward scalable graphene-based valleytronics.

3.
Anal Bioanal Chem ; 407(14): 4091-9, 2015 May.
Artigo em Inglês | MEDLINE | ID: mdl-25845527

RESUMO

This work evaluates the application of a thermodynamic model to comprehensive two-dimensional gas chromatography (GC × GC) coupled with time-of-flight mass spectrometry for anabolic agent investigation. Doping control deals with hundreds of drugs that are prohibited in sports. Drug discovery in biological matrices is a challenging task that requires powerful tools when one is faced with the rapidly changing designer drug landscape. In this work, a thermodynamic model developed for the prediction of both primary and secondary retention times in GC × GC has been applied to trimethylsilylated hydroxyl (O-TMS)- and methoxime-trimethylsilylated carbonyl (MO-TMS)-derivatized endogenous steroids. This model was previously demonstrated on a pneumatically modulated GC × GC system, and is applied for the first time to a thermally modulated GC × GC system. Preliminary one-dimensional experiments allowed the calculation of thermodynamic parameters (ΔH, ΔS, and ΔC p ) which were successfully applied for the prediction of the analytes' interactions with the stationary phases of both the first-dimension column and the second-dimension column. The model was able to predict both first-dimension and second-dimension retention times with high accuracy compared with the GC × GC experimental measurements. Maximum differences of -8.22 s in the first dimension and 0.4 s in the second dimension were encountered for the O-TMS derivatives of 11ß-hydroxyandrosterone and 11-ketoetiocholanolone, respectively. For the MO-TMS derivatives, the largest discrepancies were from testosterone (9.65 ) for the first-dimension retention times and 11-keto-etiocholanolone (0.4 s) for the second-dimension retention times.


Assuntos
Cromatografia Gasosa/métodos , Espectrometria de Massas/métodos , Esteroides/química , Termodinâmica
4.
Nat Commun ; 6: 6620, 2015 Mar 18.
Artigo em Inglês | MEDLINE | ID: mdl-25782977

RESUMO

Current methods of chemical vapour deposition (CVD) of graphene on copper are complicated by multiple processing steps and by high temperatures required in both preparing the copper and inducing subsequent film growth. Here we demonstrate a plasma-enhanced CVD chemistry that enables the entire process to take place in a single step, at reduced temperatures (<420 °C), and in a matter of minutes. Growth on copper foils is found to nucleate from arrays of well-aligned domains, and the ensuing films possess sub-nanometre smoothness, excellent crystalline quality, low strain, few defects and room-temperature electrical mobility up to (6.0±1.0) × 10(4) cm(2) V(-1) s(-1), better than that of large, single-crystalline graphene derived from thermal CVD growth. These results indicate that elevated temperatures and crystalline substrates are not necessary for synthesizing high-quality graphene.

5.
Child Care Health Dev ; 41(5): 641-53, 2015 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-25733080

RESUMO

BACKGROUND: Interventions to minimize the long-term consequences of neglect or emotional abuse rely on prompt identification of these children. This systematic review of world literature (1947-2012) identifies features that children aged 5-14 years experiencing neglect or emotional abuse, as opposed to physical or sexual abuse, may exhibit. METHODS: Searching 18 databases, utilizing over 100 keywords, supplemented by hand searching, 13,210 articles were identified and 111 underwent full critical appraisal by two independent trained reviewers. RESULTS: The 30 included studies highlighted behavioural features (15 studies), externalizing features being the most prominent (8/9 studies) and internalizing features noted in 4/6 studies. Four studies identified attention deficit hyperactivity disorder (ADHD) associated features: impulsivity, inattention or hyperactivity. Child difficulties in initiating or developing friendships were noted in seven studies. Of 13 studies addressing emotional well-being, three highlighted low self-esteem, with a perception of external control (1), or depression (6) including suicidality (1). A negative internal working model of the mother increased the likelihood of depression (1). In assessing cognition or academic performance, lower general intelligence (3/4) and reduced literacy and numeracy (2) were reported, but no observable effect on memory (3). CONCLUSIONS: School-aged children presenting with poor academic performance, ADHD symptomatology or abnormal behaviours warrant assessment of neglect or emotional abuse as a potential underlying cause.


Assuntos
Transtorno do Deficit de Atenção com Hiperatividade/diagnóstico , Maus-Tratos Infantis/psicologia , Comportamento Infantil/psicologia , Depressão/diagnóstico , Adaptação Psicológica , Adolescente , Criança , Desenvolvimento Infantil , Cognição , Escolaridade , Emoções , Humanos , Habilidades Sociais
6.
J Chromatogr A ; 1358: 225-31, 2014 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-25035236

RESUMO

Thermodynamic parameters of ΔH(T0), ΔS(T0), and ΔCP for 156 compounds comprising alkanes, alkyl halides and alcohols were determined for a 5% phenyl 95% methyl stationary phase. The determination of thermodynamic parameters relies on a Nelder-Mead simplex optimization to rapidly obtain the parameters. Two methodologies of external and leave one out cross validations were applied to assess the robustness of the estimations of thermodynamic parameters. The largest absolute errors in predicted retention time across all temperature ramps and all compounds were 1.5 and 0.3s for external and internal sets, respectively. The possibility of an in silico extension of the thermodynamic library was tested using a quantitative structure-retention relationship (QSRR) methodology. The estimated thermodynamic parameters were utilized to develop QSRR models. Individual partial least squares (PLS) models were developed for each of the three classes of the molecules. R(2) values for the test sets of all models across all temperature ramps were larger than 0.99 and the average of relative errors in retention time predictions of the test sets for alkanes, alcohols, and alkyl halides were 1.8%, 2.4%, and 2.5%, respectively.


Assuntos
Modelos Químicos , Relação Quantitativa Estrutura-Atividade , Álcoois/química , Álcoois/isolamento & purificação , Alcanos/química , Alcanos/isolamento & purificação , Cromatografia Gasosa , Entropia , Hidrocarbonetos Halogenados/química , Hidrocarbonetos Halogenados/isolamento & purificação , Análise dos Mínimos Quadrados , Temperatura
7.
J Chromatogr A ; 1330: 69-73, 2014 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-24484693

RESUMO

A new method for calibrating thermodynamic data to be used in the prediction of analyte retention times is presented. The method allows thermodynamic data collected on one column to be used in making predictions across columns of the same stationary phase but with varying geometries. This calibration is essential as slight variances in the column inner diameter and stationary phase film thickness between columns or as a column ages will adversely affect the accuracy of predictions. The calibration technique uses a Grob standard mixture along with a Nelder-Mead simplex algorithm and a previously developed model of GC retention times based on a three-parameter thermodynamic model to estimate both inner diameter and stationary phase film thickness. The calibration method is highly successful with the predicted retention times for a set of alkanes, ketones and alcohols having an average error of 1.6s across three columns.


Assuntos
Cromatografia Gasosa/normas , Álcoois/análise , Alcanos/análise , Calibragem , Cromatografia Gasosa/métodos , Cetonas/análise , Modelos Teóricos , Termodinâmica
8.
J Chromatogr A ; 1325: 204-12, 2014 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-24377740

RESUMO

A new method for estimating the thermodynamic parameters of ΔH(T0), ΔS(T0), and ΔCP for use in thermodynamic modeling of GC×GC separations has been developed. The method is an alternative to the traditional isothermal separations required to fit a three-parameter thermodynamic model to retention data. Herein, a non-linear optimization technique is used to estimate the parameters from a series of temperature-programmed separations using the Nelder-Mead simplex algorithm. With this method, the time required to obtain estimates of thermodynamic parameters a series of analytes is significantly reduced. This new method allows for precise predictions of retention time with the average error being only 0.2s for 1D separations. Predictions for GC×GC separations were also in agreement with experimental measurements; having an average relative error of 0.37% for (1)tr and 2.1% for (2)tr.


Assuntos
Cromatografia Gasosa/métodos , Termodinâmica , Algoritmos , Cromatografia Gasosa/instrumentação , Temperatura , Fatores de Tempo
10.
J Sep Sci ; 35(17): 2228-32, 2012 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-22753143

RESUMO

Thermodynamic modeling of retention times in gas chromatography depends on the accurate estimation of thermodynamic parameters. Previous research has used manual injections of samples with coinjection of a dead time marker to obtain accurate measurements of the retention factor of analytes. Ideally this process would be automated. Herein an approach is presented by which thermodynamic parameters can be estimated both autonomously and accurately. This method also allows for a consistent estimation of thermodynamic parameters regardless of factors such as data system delays and the nature of the void time marker employed. Ignoring these factors can lead to significant errors in the prediction of retention times when using thermodynamic models.

11.
J Chromatogr A ; 1255: 184-9, 2012 Sep 14.
Artigo em Inglês | MEDLINE | ID: mdl-22386257

RESUMO

A method was developed to accurately predict both the primary and secondary retention times for a series of alkanes, ketones and alcohols in a flow-modulated GC×GC system. This was accomplished through the use of a three-parameter thermodynamic model where ΔH, ΔS, and ΔC(p) for an analyte's interaction with the stationary phases in both dimensions are known. Coupling this thermodynamic model with a time summation calculation it was possible to accurately predict both (1)t(r) and (2)t(r) for all analytes. The model was able to predict retention times regardless of the temperature ramp used, with an average error of only 0.64% for (1)t(r) and an average error of only 2.22% for (2)t(r). The model shows promise for the accurate prediction of retention times in GC×GC for a wide range of compounds and is able to utilize data collected from 1D experiments.


Assuntos
Cromatografia Gasosa/métodos , Modelos Teóricos , Compostos Orgânicos/análise , Compostos Orgânicos/química , Compostos Orgânicos/isolamento & purificação , Termodinâmica
12.
J Chromatogr A ; 1255: 12-23, 2012 Sep 14.
Artigo em Inglês | MEDLINE | ID: mdl-22364667

RESUMO

Petroleum analysis presents many unique challenges as a result of the overwhelming number of compounds present in petroleum samples. Consequently the use of multidimensional separation techniques will almost invariably be required in order to overcome these challenges. Within this paper we review recent developments in the application of comprehensive multidimensional techniques for petroleum analysis focusing on more recent applications. Basic instrumentation for various comprehensive multidimensional techniques is outlined along with an overview of a broad range of applications in both group-type and target molecule analyses for petroleum and biofuel analysis. In addition, strategies for data interpretation and chemometric analysis of multidimensional data are also reviewed.


Assuntos
Fracionamento Químico/métodos , Cromatografia Líquida/métodos , Petróleo/análise
13.
J Thromb Haemost ; 10(2): 229-35, 2012 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-22188037

RESUMO

BACKGROUND: Patients undergoing neurosurgical procedures are at risk of venous thromboembolism (VTE), but often have contraindications for anticoagulant prophylaxis. OBJECTIVES: To assess the efficacy and tolerability of a new, lightweight, portable, battery-powered, intermittent calf compression device, Venowave, for the prevention of VTE in neurosurgical inpatients. PATIENTS/METHODS: We performed an open randomized controlled trial comparing Venowave with control for the prevention of VTE in patients undergoing neurosurgery. The primary outcome was the composite of asymptomatic deep vein thrombosis (DVT) detected by screening venography or compression ultrasound performed on day 9 (± 2 days) and symptomatic VTE. RESULTS: We randomized 75 patients to receive Venowave devices and 75 to the control group. All patients were prescribed graduated compression stockings and physiotherapy. VTE occurred in three patients randomized to Venowave and in 14 patients randomized to control (4.0% vs. 18.7%, relative risk 0.21; 95% confidence interval 0.05-0.75, P = 0.008). Similar reductions were seen for proximal DVT (2.7% vs. 8.0%) and symptomatic VTE (0% vs. 2.7%), and the results were consistent in all subgroups examined. CONCLUSIONS: Venowave devices are effective in preventing VTE in high-risk neurosurgical patients.


Assuntos
Dispositivos de Compressão Pneumática Intermitente , Procedimentos Neurocirúrgicos/efeitos adversos , Trombose Venosa/prevenção & controle , Idoso , Terapia Combinada , Desenho de Equipamento , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Flebografia , Modalidades de Fisioterapia , Pressão , Medição de Risco , Fatores de Risco , Meias de Compressão , Fatores de Tempo , Resultado do Tratamento , Ultrassonografia , Trombose Venosa/diagnóstico por imagem , Trombose Venosa/etiologia
14.
Phys Rev Lett ; 106(8): 087004, 2011 Feb 25.
Artigo em Inglês | MEDLINE | ID: mdl-21405593

RESUMO

Scanning tunneling spectroscopic studies of Ba(Fe(1-x)Co(x))(2)As(2) (x=0.06, 0.12) single crystals reveal direct evidence for predominantly two-gap superconductivity. These gaps decrease with increasing temperature and vanish above the superconducting transition T(c). The two-gap nature and the slightly doping- and energy-dependent quasiparticle scattering interferences near the wave vectors (±π, 0) and (0, ±π) are consistent with sign-changing s-wave superconductivity. The excess zero-bias conductance and the large gap-to-T(c) ratios suggest dominant unitary impurity scattering.

15.
J Chromatogr A ; 1218(21): 3241-6, 2011 May 27.
Artigo em Inglês | MEDLINE | ID: mdl-20965509

RESUMO

We present an investigation into the influence of carrier gas on the thermodynamics governing a capillary gas chromatographic separation. Thermodynamic parameters are estimated for a series of alkanes and alcohols on three common stationary phases using helium, hydrogen, and nitrogen carrier gases. It is shown that the substitution of carrier gases for one another results in a change in the thermodynamic parameters governing the separation. The effect of the carrier gas on the thermodynamic parameters is large enough to compromise the accuracy of the retention time calculations based on thermodynamic parameters collected in a carrier gas other than the one actually in use in a specific gas chromatographic system. A possible kinetic explanation for these observations is also investigated.


Assuntos
Cromatografia Gasosa/métodos , Gases/química , Álcoois/química , Alcanos/química , Hélio/química , Hidrogênio/química , Cinética , Nitrogênio/química , Termodinâmica
16.
Analyst ; 135(10): 2688-93, 2010 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-20714522

RESUMO

The cationic surfactants didodecyldimethylammonium bromide (DDAB) and dioctadecyldimethyl-ammonium bromide (DODAB) have previously been shown to form semi-permanent coatings that effectively prevent adsorption of cationic proteins in fused silica capillaries with inner diameters of 25-75 µm. This paper investigates the impact that narrower capillary diameters (≤25 µm) have on the stability of surfactant bilayer coatings and the efficiency of separations of model cationic proteins and neurotransmitters. Using a DODAB-coated 5 µm i.d. capillary 210 consecutive protein separations (1050 min) were performed without recoating the capillary between runs. Separation efficiencies of 1,400,000-2,000,000 plates per m (340,000-430,000 plates) were obtained. Migration time reproducibilites of 6.8% RSD were observed for 300 injections performed over a 30 day period without any regeneration of the coating. Neurotransmitters were separated with efficiencies ranging from 470,000-610,000 plates per m (110,000-140,000 plates) in a 5 µm capillary.

18.
Nano Lett ; 9(7): 2542-6, 2009 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-19534500

RESUMO

Graphene has emerged as an electronic material that is promising for device applications and for studying two-dimensional electron gases with relativistic dispersion near two Dirac points. Nonetheless, deviations from Dirac-like spectroscopy have been widely reported with varying interpretations. Here we show evidence for strain-induced spatial modulations in the local conductance of single-layer graphene on SiO(2) substrates from scanning tunneling microscopic (STM) studies. We find that strained graphene exhibits parabolic, U-shaped conductance vs bias voltage spectra rather than the V-shaped spectra expected for Dirac fermions, whereas V-shaped spectra are recovered in regions of relaxed graphene. Strain maps derived from the STM studies further reveal direct correlation with the local tunneling conductance. These results are attributed to a strain-induced frequency increase in the out-of-plane phonon mode that mediates the low-energy inelastic charge tunneling into graphene.


Assuntos
Eletrônica , Elétrons , Grafite/química , Dióxido de Silício/química , Condutividade Elétrica , Gases , Teste de Materiais , Microscopia Eletrônica de Varredura , Propriedades de Superfície
19.
Int J Lab Hematol ; 31(2): 180-8, 2009 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-18190586

RESUMO

In some mild haemophilia A patients (discrepant phenotype), coagulation FVIII levels by one-stage assay (FVIII-1st) are more than double those by classical two-stage coagulation assay (FVIII-2st), and may fall within the normal range. Our aim was to assess automated two-stage chromogenic FVIII assays (FVIII-chr) for diagnosis of mild discrepant haemophilia A. Three chromogenic FVIII kits (Biophen, Coamatic and Dade-Behring) were evaluated, using recommended and extended incubation times. Samples were tested from patients with discrepant haemophilia (n = 7) and equivalent mild haemophilia (agreement between FVIII-1st and FVIII-2st, n = 4). For equivalent haemophilia, FVIII-chr were consistent with FVIII-1st and FVIII-2st for all kits at all incubation times. For discrepant haemophilia, using recommended incubation times, mean FVIII-chr using Biophen reagents was 22 IU/dl (range 13-31), with Coamatic 26 (17-34) and with Dade-Behring 41 (33-47), compared with 36 (27-44) for FVIII-1st and 8 (6-9) for FVIII-2st. FVIII-chr decreased as incubation time was increased with Biophen and Coamatic, but decreased less with Dade-Behring. FVIII-chr using the Dade-Behring kit gave similar results to FVIII-1st and is not suitable for diagnosis of mild discrepant haemophilia A. FVIII-chr by Biophen and Coamatic kits is suitable for diagnosis of these patients, especially with an extended incubation time.


Assuntos
Fator VIII/análise , Hemofilia A/diagnóstico , Kit de Reagentes para Diagnóstico , Coagulação Sanguínea/fisiologia , Fator VIII/genética , Hemofilia A/sangue , Humanos , Mutação/genética
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