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1.
Hernia ; 27(4): 861-871, 2023 08.
Artigo em Inglês | MEDLINE | ID: mdl-37368183

RESUMO

PURPOSE: Incisional hernias are common after laparotomies. The aims of this study were to assess the rate of incisional hernia repair after abdominal surgery, recurrence rate, hospital costs, and risk factors, in France. METHODS: This national, retrospective, longitudinal, observational study was based on the exhaustive hospital discharge database (PMSI). All adult patients (≥ 18 years old) hospitalised for an abdominal surgical procedure between 01-01-2013 and 31-12-2014 and hospitalised for incisional hernia repair within five years were included. Descriptive analyses and cost analyses from the National Health Insurance (NHI) viewpoint (hospital care for the hernia repair) were performed. To identify risk factors for hernia repair a multivariable Cox model and a machine learning analysis were performed. RESULTS: In 2013-2014, 710074 patients underwent abdominal surgery, of which 32633 (4.6%) and 5117 (0.7%) had ≥ 1 and ≥ 2 incisional hernia repair(s) within five years, respectively. Mean hospital costs amounted to €4153/hernia repair, representing nearly €67.7 million/year. Some surgical sites exposed patients at high risk of incisional hernia repair: colon and rectum (hazard ratio [HR] 1.2), and other sites on the small bowel and the peritoneum (HR 1.4). Laparotomy procedure and being ≥ 40 years old put patients at high risk of incisional hernia repair even when operated on low-risk sites such as stomach, duodenum, and hepatobiliary. CONCLUSION: The burden of incisional hernia repair is high and most patients are at risk either due to age ≥ 40 or the surgery site. New approaches to prevent the onset of incisional hernia are warranted.


Assuntos
Hérnia Ventral , Hérnia Incisional , Adulto , Humanos , Adolescente , Hérnia Incisional/epidemiologia , Hérnia Incisional/etiologia , Hérnia Incisional/cirurgia , Estudos Retrospectivos , Incidência , Herniorrafia/efeitos adversos , Herniorrafia/métodos , Hérnia Ventral/cirurgia , Peritônio/cirurgia , Fatores de Risco , Telas Cirúrgicas/efeitos adversos
2.
J Chem Phys ; 153(4): 044117, 2020 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-32752716

RESUMO

Provided in this paper is a theory of long-range electron transfer with near sound (supersonic or subsonic) velocity along one-dimensional crystal lattices. The theory represents the development of an earlier work by introducing Marcus formulation. To illustrate its application to a realistic case, the theory is used to offer an explanation of two puzzling observations made by Donovan and Wilson in transient photoconduction experiments with non-dopable perfectly crystalline polydiacetylene crystals in the presence of an electric field: transport velocity value close to sound velocity being independent of field for four orders of magnitude of field (102 V/m-106 V/m) and, in the low field values, an ultra-high mobility greater than 20 m2/V s. We also study factors eventually leading to lowering of the transport velocity.

3.
J Phys Chem A ; 123(30): 6439-6454, 2019 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-31329443

RESUMO

For some values of the total angular momentum consistent with reaction, the title processes involve nonreactive trajectories proceeding through a single rebound mechanism during which the internal motion of the reagent diatom is nearly unperturbed. When such paths are in a significant amount, the classical reaction probability is found to be markedly lower than the quantum mechanical one. This finding was recently attributed to an unusual quantum effect called diffraction-mediated trapping, and a semiclassical correction was proposed in order to take into account this effect in the classical trajectory method. In the present work, we apply the resulting approach to the calculation of opacity functions as well as total and state-resolved integral cross sections (ICSs) and compare the values obtained with exact quantum ones, most of which are new. As the title reactions proceed through a deep insertion well, mean potential statistical calculations are also presented. Seven values of the collision energy, ranging from 30 to 1127 K, are considered. Two remarkable facts stand out: (i) The corrected classical treatment strongly improves the accuracy of the opacity function as compared to the usual classical treatment. When the entrance transition state is tight, however, those trajectories crossing it with a bending vibrational energy below the zero point energy must be discarded. (ii) The quantum opacity function, particularly its cutoff, is finely reproduced by the statistical approach. Consequently, the total ICS is also very well described by the two previous approximate methods. These, however, do not predict state-resolved ICSs with the same accuracy, proving thereby that (i) one or several genuine quantum effects involved in the dynamics are missed by the corrected classical treatment and (ii) the dynamics are not fully statistical.

4.
Biosens Bioelectron ; 132: 90-96, 2019 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-30856432

RESUMO

The present work is dedicated to the development of a lab-on-chip (LOC) device for water toxicity environmental analysis and more especially herbicide detection. The final goal is focused on the functional integration of three-electrode electrochemical microcells (ElecCell) and organic photodetectors (OPD) in order to perform simultaneously electrochemical and optical detection in the frame of algal metabolism monitoring. Considering three different algae, ie. Chlamydomonas reinhardtii, Pseudokirchneriella subcapitata and Chlorella vulgaris while dealing with photosynthesis, the multi-microsensor platform enables to measure the variations of microalgae fluorescence as well as oxygen production. It is applied to study the Diuron herbicide influences on algal metabolism, evidencing fluorescence enhancement and oxygen production inhibition for concentrations as low as few tens of nanomoles. These results are performed with unconcentrated and six time concentrated algae solutions respectively, to estimate the ability of this dual-sensor system to conduct measurements without any sample preparation. Thus, according to the obtained results, the proposed LOC device is fully adapted to the electrochemical/optical dual detection for on-site pollutant analysis, ie. without sample pre-treatment.


Assuntos
Técnicas Biossensoriais/instrumentação , Diurona/análise , Herbicidas/análise , Dispositivos Lab-On-A-Chip , Poluentes Químicos da Água/análise , Chlamydomonas reinhardtii/metabolismo , Chlorella vulgaris/metabolismo , Diurona/metabolismo , Técnicas Eletroquímicas/instrumentação , Desenho de Equipamento , Fluorescência , Herbicidas/metabolismo , Microalgas/metabolismo , Oxigênio/metabolismo , Fotossíntese , Poluentes Químicos da Água/metabolismo
5.
Phys Chem Chem Phys ; 19(42): 28555-28571, 2017 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-29063941

RESUMO

We present an experimental and theoretical investigation of the deactivation rate of S(1D) atoms by collisions with argon. Kinetic measurements were performed at temperatures from 5.8 K to 298 K in cold uniform supersonic flows using a CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in a Uniform Supersonic Flow) apparatus. In order to simulate them, ab initio electronic structure calculations using internally contracted MRCI methodology were performed to describe the interaction. Starting from them, close-coupling calculations were carried out to determine collisional quenching probabilities for the transition S(1D) → S(3P) in the energy range 1-3000 K (1 K ≈ 0.7 cm-1), sufficient to calculate thermal rate coefficients up to 300 K. Stückelberg-like oscillations in the quenching probabilities as a function of the energy are found and interpreted using a semiclassical model. Differences between the temperature dependence of the experimental and theoretical rate coefficients are detected at low temperatures. They are discussed in the light of a study of the high sensitivity of the theoretical results to the potential curves, due to the interference mechanisms which underlie the process.

7.
Int J Cardiol ; 226: 53-59, 2017 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-27788390

RESUMO

Heart failure can be associated with inflammation but it is unclear if inflammation is directly related to hemodynamic worsening or is an independent pathway. Our aim was to investigate inflammation and mechanical stress using serial measurements of biomarkers in acute and chronic heart failure with reduced ejection fraction (AHF and CHF). METHOD: The following biomarkers were measured on admission, at discharge and one month after discharge: B-type natriuretic peptide (BNP), high-sensitivity C-Reactive protein (hsCRP), Tumour Necrosis Factor alpha (TNFα), interleukin 6 (IL6), myeloperoxidase (MPO), suppression of tumorigenicity 2 (ST2), mid-regional pro-adrenomedullin (MR-proADM), galectin 3 (Gal3), Growth differentiating factor 15 (GDF15) and procalcitonin (PCT). RESULTS: In control CHF group (n=20, 69±11y, NYHA 1-2), most biomarker levels were low and stable over time. In AHF (n=55, 71±14y), BNP, ST2 and GDF15 levels were highly increased on admission and then decreased rapidly with clinical improvement; BNP, ST2 and GDF15 levels were statistically correlated (r=0.64, 0.46 and 0.39; p<0.001 for both). Both hsCRP, MPO, TNFα and Gal3 levels were increased in most AHF patients (70, 56, 83 and 98% respectively) with poor change over time. HsCRP, MPO and TNFα levels were correlated. IL6, MR-proADM and PCT levels were slightly increased, without change over time. Highest quartiles of BNP and ST2 were associated with death or readmission at one year (HR 2.33 [95CI 1.13-4.80] and 2.42 [1.27-4.60]). CONCLUSION: AHF is associated with systemic inflammation. This inflammatory response continued up to one month after discharge despite normalisation of mechanical stress-related markers.


Assuntos
Insuficiência Cardíaca/sangue , Insuficiência Cardíaca/fisiopatologia , Mediadores da Inflamação/sangue , Volume Sistólico/fisiologia , Adrenomedulina/sangue , Idoso , Biomarcadores/sangue , Proteína C-Reativa/metabolismo , Feminino , Seguimentos , Insuficiência Cardíaca/diagnóstico , Humanos , Inflamação/sangue , Inflamação/diagnóstico , Inflamação/fisiopatologia , Masculino , Pessoa de Meia-Idade , Peptídeo Natriurético Encefálico/sangue
8.
Allergy ; 71(3): 416-20, 2016 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-26841279

RESUMO

The main metabolism pathway of tryptophan is protein formation, but it can also be metabolized into serotonin and kynurenine. Indoleamine 2,3-dioxygenase (IDO) is the enzyme that catalyzes the degradation of tryptophan into kynurenine. Mastocytosis is a heterogeneous disease characterized by mast cell accumulation in various tissues with 57% of patients having gastrointestinal involvement. We studied tryptophan metabolism in mastocytosis patients displaying or not gastrointestinal features and healthy subjects (n = 26 in each group). Mastocytosis patients with digestive symptoms displayed significantly increased kynurenine level and IDO activity as compared to healthy controls and mastocytosis patients without digestive symptoms. This could be linked to mast cell-mediated digestive inflammation among patients with mastocytosis. This work is the first focusing on kynurenine pathway in a mast cell disease and could help to understand the pathogenesis of digestive features in mastocytosis as well as in other mast cell-mediated diseases.


Assuntos
Sistema Digestório/metabolismo , Cinurenina/sangue , Mastocitose/sangue , Mastocitose/diagnóstico , Triptofano/sangue , Biomarcadores , Estudos de Casos e Controles , Sistema Digestório/patologia , Feminino , Humanos , Indolamina-Pirrol 2,3,-Dioxigenase/sangue , Masculino
9.
Mol Psychiatry ; 21(11): 1511-1516, 2016 11.
Artigo em Inglês | MEDLINE | ID: mdl-26809839

RESUMO

Converging sources of evidence point to a role for inflammation in the development of depression, fatigue and cognitive dysfunction. More precisely, the tryptophan (TRP) catabolism is thought to play a major role in inflammation-induced depression. Mastocytosis is a rare disease in which chronic symptoms, including depression, are related to mast cell accumulation and activation. Our objectives were to study the correlations between neuropsychiatric features and the TRP catabolism pathway in mastocytosis in order to demonstrate mast cells' potential involvement in inflammation-induced depression. Fifty-four patients with mastocytosis and a mean age of 50.1 years were enrolled in the study and compared healthy age-matched controls. Depression and stress were evaluated with the Beck Depression Inventory revised and the Perceived Stress Scale. All patients had measurements of TRP, serotonin (5-HT), kynurenine (KYN), indoleamine 2,3-dioxygenase 1 (IDO1) activity (ratio KYN/TRP), kynurenic acid (KA) and quinolinic acid (QA). Patients displayed significantly lower levels of TRP and 5-HT without hypoalbuminemia or malabsorption, higher IDO1 activity, and higher levels of KA and QA, with an imbalance towards the latter. High perceived stress and high depression scores were associated with low TRP and high IDO1 activity. In conclusion, TRP metabolism is altered in mastocytosis and correlates with perceived stress and depression, demonstrating mast cells' involvement in inflammation pathways linked to depression.


Assuntos
Depressão/metabolismo , Mastócitos/metabolismo , Triptofano/metabolismo , Transtorno Depressivo Maior/metabolismo , Feminino , Humanos , Indolamina-Pirrol 2,3,-Dioxigenase , Inflamação/metabolismo , Ácido Cinurênico , Cinurenina , Masculino , Mastócitos/fisiologia , Mastocitose/metabolismo , Pessoa de Meia-Idade , Escalas de Graduação Psiquiátrica , Serotonina , Estresse Psicológico , Triptofano/fisiologia
10.
Biosens Bioelectron ; 79: 568-73, 2016 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-26749098

RESUMO

The present work was dedicated to the development of a lab-on-chip device for water toxicity analysis and more particularly herbicide detection in water. It consists in a portable system for on-site detection composed of three-electrode electrochemical microcells, integrated on a fluidic platform constructed on a glass substrate. The final goal is to yield a system that gives the possibility of conducting double, complementary detection: electrochemical and optical and therefore all materials used for the fabrication of the lab-on-chip platform were selected in order to obtain a device compatible with optical technology. The basic detection principle consisted in electrochemically monitoring disturbances in metabolic photosynthetic activities of algae induced by the presence of Diuron herbicide. Algal response, evaluated through oxygen (O2) monitoring through photosynthesis was different for each herbicide concentration in the examined sample. A concentration-dependent inhibition effect of the herbicide on photosynthesis was demonstrated. Herbicide detection was achieved through a range (blank - 1 µM Diuron herbicide solution) covering the limit of maximum acceptable concentration imposed by Canadian government (0.64 µM), using a halogen white light source for the stimulation of algal photosynthetic apparatus. Superior sensitivity results (limit of detection of around 0.1 µM) were obtained with an organic light emitting diode (OLED), having an emission spectrum adapted to algal absorption spectrum and assembled on the final system.


Assuntos
Técnicas Biossensoriais/instrumentação , Diurona/análise , Herbicidas/análise , Dispositivos Lab-On-A-Chip , Microalgas/fisiologia , Poluentes Químicos da Água/análise , Diurona/metabolismo , Técnicas Eletroquímicas/instrumentação , Herbicidas/metabolismo , Microalgas/efeitos dos fármacos , Fotossíntese/efeitos dos fármacos , Poluentes Químicos da Água/metabolismo , Qualidade da Água
11.
J Chem Phys ; 143(20): 204305, 2015 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-26627957

RESUMO

Quantum reactive and elastic cross sections and rate coefficients have been calculated for D(+) + H2 (v = 0, j = 0) collisions in the energy range from 10(-8) K (deep ultracold regime), where only one partial wave is open, to 150 K (Langevin regime) where many of them contribute. In systems involving ions, the ∼R(-4) behavior extends the interaction up to extremely long distances, requiring a special treatment. To this purpose, we have used a modified version of the hyperspherical quantum reactive scattering method, which allows the propagations up to distances of 10(5) a0 needed to converge the elastic cross sections. Interpolation procedures are also proposed which may reduce the cost of exact dynamical calculations at such low energies. Calculations have been carried out on the PES by Velilla et al. [J. Chem. Phys. 129, 084307 (2008)] which accurately reproduces the long range interactions. Results on its prequel, the PES by Aguado et al. [J. Chem. Phys. 112, 1240 (2000)], are also shown in order to emphasize the significance of the inclusion of the long range interactions. The calculated reaction rate coefficient changes less than one order of magnitude in a collision energy range of ten orders of magnitude, and it is found in very good agreement with the available experimental data in the region where they exist (10-100 K). State-to-state reaction probabilities are also provided which show that for each partial wave, the distribution of HD final states remains essentially constant below 1 K.

12.
Transl Psychiatry ; 4: e479, 2014 Nov 11.
Artigo em Inglês | MEDLINE | ID: mdl-25386956

RESUMO

Elevated whole-blood serotonin and decreased plasma melatonin (a circadian synchronizer hormone that derives from serotonin) have been reported independently in patients with autism spectrum disorders (ASDs). Here, we explored, in parallel, serotonin, melatonin and the intermediate N-acetylserotonin (NAS) in a large cohort of patients with ASD and their relatives. We then investigated the clinical correlates of these biochemical parameters. Whole-blood serotonin, platelet NAS and plasma melatonin were assessed in 278 patients with ASD, their 506 first-degree relatives (129 unaffected siblings, 199 mothers and 178 fathers) and 416 sex- and age-matched controls. We confirmed the previously reported hyperserotonemia in ASD (40% (35-46%) of patients), as well as the deficit in melatonin (51% (45-57%)), taking as a threshold the 95th or 5th percentile of the control group, respectively. In addition, this study reveals an increase of NAS (47% (41-54%) of patients) in platelets, pointing to a disruption of the serotonin-NAS-melatonin pathway in ASD. Biochemical impairments were also observed in the first-degree relatives of patients. A score combining impairments of serotonin, NAS and melatonin distinguished between patients and controls with a sensitivity of 80% and a specificity of 85%. In patients the melatonin deficit was only significantly associated with insomnia. Impairments of melatonin synthesis in ASD may be linked with decreased 14-3-3 proteins. Although ASDs are highly heterogeneous, disruption of the serotonin-NAS-melatonin pathway is a very frequent trait in patients and may represent a useful biomarker for a large subgroup of individuals with ASD.


Assuntos
Transtornos Globais do Desenvolvimento Infantil/sangue , Melatonina/sangue , Serotonina/análogos & derivados , Serotonina/sangue , Transdução de Sinais/fisiologia , Adolescente , Adulto , Biomarcadores/sangue , Criança , Transtornos Globais do Desenvolvimento Infantil/genética , Feminino , Humanos , Masculino , Pais , Irmãos
13.
Biosens Bioelectron ; 61: 290-7, 2014 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-24906088

RESUMO

An autonomous electrochemical biosensor with three electrodes integrated on the same silicon chip dedicated to the detection of herbicides in water was fabricated by means of silicon-based microfabrication technology. Platinum (Pt), platinum black (Pt Bl), tungsten/tungsten oxide (W/WO3) and iridium oxide (Pt/IrO2) working ultramicroelectrodes were developed. Ag/AgCl and Pt electrodes were used as reference and counter-integrated electrodes respectively. Physical vapor deposition (PVD) and electrodeposition were used for thin film deposition. The ultramicroelectrodes were employed for the detection of O2, H2O2 and pH related ions H3O(+)/OH(-), species taking part in photosynthetic and metabolic activities of algae. By measuring the variations in consumption-production rates of these electroactive species by algae, the quantity of herbicides present at trace level in the solution can be estimated. Fabricated ultramicroelectrodes were electrochemically characterized and calibrated. Pt Black ultramicroelectrodes exhibited the greatest sensitivity regarding O2 and H2O2 detection while Pt/IrO2 ultramicroelectrodes were more sensitive for pH measurement compared to W/WO3 ultramicroelectrodes for pH measurement. Bioassays were then conducted to detect traces of Diuron herbicide in water samples by evaluating disturbances in photosynthetic and metabolic activities of algae caused by this herbicide.


Assuntos
Técnicas Biossensoriais/instrumentação , Chlamydomonas reinhardtii/metabolismo , Diurona/análise , Técnicas Eletroquímicas/instrumentação , Herbicidas/análise , Poluentes Químicos da Água/análise , Diurona/metabolismo , Desenho de Equipamento , Herbicidas/metabolismo , Peróxido de Hidrogênio/análise , Peróxido de Hidrogênio/metabolismo , Limite de Detecção , Microeletrodos , Oxigênio/análise , Oxigênio/metabolismo , Poluentes Químicos da Água/metabolismo
14.
Phytopathology ; 104(6): 586-96, 2014 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-24283538

RESUMO

Although bacterial wilt remains a major plant disease throughout South America and the Caribbean, the diversity of prevalent Ralstonia solanacearum populations is largely unknown. The genetic and phenotypic diversity of R. solanacearum strains in French Guiana was assessed using diagnostic polymerase chain reactions and sequence-based (egl and mutS) genotyping on a 239-strain collection sampled on the families Solanaceae and Cucurbitaceae, revealing an unexpectedly high diversity. Strains were distributed within phylotypes I (46.9%), IIA (26.8%), and IIB (26.3%), with one new endoglucanase sequence type (egl ST) found within each group. Phylotype IIB strains consisted mostly (97%) of strains with the emerging ecotype (IIB/sequevar 4NPB). Host range of IIB/4NPB strains from French Guiana matched the original emerging reference strain from Martinique. They were virulent on cucumber; virulent and highly aggressive on tomato, including the resistant reference Hawaii 7996; and only controlled by eggplant SM6 and Surya accessions. The emerging ecotype IIB/4NPB is fully established in French Guiana in both cultivated fields and uncultivated forest, rendering the hypothesis of introduction via ornamental or banana cuttings unlikely. Thus, this ecotype may have originated from the Amazonian region and spread throughout the Caribbean region.


Assuntos
Cucurbitaceae/microbiologia , Variação Genética , Genoma Bacteriano/genética , Doenças das Plantas/microbiologia , Ralstonia solanacearum/genética , Solanaceae/microbiologia , Proteínas de Bactérias/genética , DNA Bacteriano/química , DNA Bacteriano/genética , Ecótipo , Guiana Francesa , Genótipo , Geografia , Especificidade de Hospedeiro , Tipagem Molecular , Fenótipo , Filogenia , Reação em Cadeia da Polimerase , Ralstonia solanacearum/classificação , Ralstonia solanacearum/isolamento & purificação , Ralstonia solanacearum/patogenicidade , Análise de Sequência de DNA , Virulência
15.
Cell Death Dis ; 4: e456, 2013 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-23303130

RESUMO

The subversion of the normal function exerted by the cellular prion protein (PrP(C)) in neurons by pathogenic prions is assumed to have a central role in the pathogenesis of transmissible spongiform encephalopathies. Using two murine models of prion infection, the 1C11 neuronal cell line and neurospheres, we document that prion infection is associated with the constitutive activation of signaling targets normally coupled with PrP(C), including the Fyn kinase, the mitogen-associated protein kinases ERK1/2 and the CREB transcription factor. PrP(C)-dependent signaling overactivation in infected cells is associated with the recruitment of p38 and JNK stress-associated kinases. Downstream from CREB, prion-infected cells exhibit reduced activity of the matrix metalloprotease (MMP)-9. As MMP-9 catalyzes the degradation of the amyloid A-beta peptide, the decrease in MMP-9 activity in prion-infected cells causes a significant impairment of the clearance of A-beta, leading to its accumulation. By exploiting two 1C11-infected clones accumulating high or moderate levels of prions, we show that the prion-induced changes are correlated with the level of infectivity. Of note, a dose-dependent increase in A-beta levels was also found in the cerebrospinal fluid of mice inoculated with these infected clones. By demonstrating that pathogenic prions trigger increases in A-beta levels through the deviation of PrP(C) signaling, our data argue that A-beta may exacerbate prion-induced toxicity.


Assuntos
Peptídeos beta-Amiloides/metabolismo , Neurônios/metabolismo , Proteínas PrPC/metabolismo , Príons/metabolismo , Peptídeos beta-Amiloides/líquido cefalorraquidiano , Animais , Linhagem Celular , Proteína de Ligação ao Elemento de Resposta ao AMP Cíclico/metabolismo , Proteína 1 de Resposta de Crescimento Precoce/metabolismo , Proteínas Quinases JNK Ativadas por Mitógeno/metabolismo , Metaloproteinase 9 da Matriz/metabolismo , Camundongos , Proteína Quinase 1 Ativada por Mitógeno/metabolismo , Proteína Quinase 3 Ativada por Mitógeno/metabolismo , Neurônios/citologia , Fosforilação , Doenças Priônicas/metabolismo , Doenças Priônicas/patologia , Proteínas Proto-Oncogênicas c-fyn/antagonistas & inibidores , Proteínas Proto-Oncogênicas c-fyn/genética , Proteínas Proto-Oncogênicas c-fyn/metabolismo , Interferência de RNA , RNA Interferente Pequeno/metabolismo , Transdução de Sinais , Proteínas Quinases p38 Ativadas por Mitógeno/metabolismo
16.
Biosens Bioelectron ; 40(1): 291-6, 2013 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-23017683

RESUMO

In this work, we report on ElecFET (Electrochemical Field Effect Transistor) devices potentially of interest for the detection of different molecules in solution. ElecFET are electrochemical microsensors in liquid phase, based on two elements: (i) a pH-sensitive chemical field effect transistor (pH-ChemFET) and (ii) a metallic microelectrode deposited around the sensitive gate. The coexistence of these two elements combines (i) potentiometric and (ii) amperometric detection effects at the microscale. Design, fabrication and experimental validation of ElecFETs based on silicon and polymer micro-technologies, are reported. We first demonstrate the detection of hydrogen peroxide (H(2)O(2)) in solution, showing a sensitivity of 5 mV/mM in the [10-100 mM] concentration range. The ElecFET concept is then extended to the detection of glucose and lactate in the [1-30 mM] and [1-6 mM] concentration range respectively. The sensitivities are between 2-6 mV/mM and 8-20 mV/mM respectively.


Assuntos
Técnicas Biossensoriais/instrumentação , Condutometria/instrumentação , Glucose/análise , Ácido Láctico/análise , Transistores Eletrônicos , Desenho de Equipamento , Análise de Falha de Equipamento , Concentração de Íons de Hidrogênio , Íons , Reprodutibilidade dos Testes , Sensibilidade e Especificidade
17.
J Chem Phys ; 137(16): 164314, 2012 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-23126717

RESUMO

Cumulative reaction probabilities (CRPs) at various total angular momenta have been calculated for the barrierless reaction S((1)D) + H(2) → SH + H at total energies up to 1.2 eV using three different theoretical approaches: time-independent quantum mechanics (QM), quasiclassical trajectories (QCT), and statistical quasiclassical trajectories (SQCT). The calculations have been carried out on the widely used potential energy surface (PES) by Ho et al. [J. Chem. Phys. 116, 4124 (2002)] as well as on the recent PES developed by Song et al. [J. Phys. Chem. A 113, 9213 (2009)]. The results show that the differences between these two PES are relatively minor and mostly related to the different topologies of the well. In addition, the agreement between the three theoretical methodologies is good, even for the highest total angular momenta and energies. In particular, the good accordance between the CRPs obtained with dynamical methods (QM and QCT) and the statistical model (SQCT) indicates that the reaction can be considered statistical in the whole range of energies in contrast with the findings for other prototypical barrierless reactions. In addition, total CRPs and rate coefficients in the range of 20-1000 K have been calculated using the QCT and SQCT methods and have been found somewhat smaller than the experimental total removal rates of S((1)D).

18.
Eur J Appl Physiol ; 112(9): 3239-50, 2012 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-22230918

RESUMO

To study the effects of a 29-h total sleep deprivation (TSD) on local cold tolerance, 10 healthy men immersed their right hand for 30 min in a 5°C water bath (CWI) after a 30-min rest period in a thermoneutral environment (Control), after a normal night (NN) and after a 29-h TSD. CWI was followed by a 30-min passive rewarming (Recovery). Finger 2 and 4 skin temperatures (Tfi2, Tfi4) and finger 2 cutaneous vascular conductance (CVC) were monitored to study cold-induced vasodilation (CIVD). Rectal temperature (Tre), mean skin temperature ([Formula: see text]), heart rate (HR) and blood pressure (BP) were also measured. Blood samples were collected at the end of the Control, at the lower and at the first maximal Tfi2 values during CWI and at Recovery. Tfi2, Tfi4 and CVC did not differ after TSD at Control, whereas they were reduced during CWI (-2.6 ± 0.7°C for Tfi2; -2 ± 0.8°C for Tfi4, -79 ± 25% for relative CVC, P < 0.05) as during Recovery (-4.9 ± 1.9°C for Tfi2, -2.6 ± 1.8°C for Tfi4, -70 ± 22% for relative CVC, P < 0.05). After TSD, the lower CVC values appeared earlier during CWI (-59 ± 19.6 s, P < 0.05). After TSD at Control and CWI, plasma endothelin levels were higher and negatively correlated with Tfi2, Tfi4 and CVC. However, no effect of TSD was found on the number and amplitude of CIVD and in Tre, HR, BP and catecholamines, for all periods. We concluded that TSD induced thermal and vascular changes in the hand which impair the local cold tolerance, suggesting that TSD increases the risk of local cold injuries.


Assuntos
Adaptação Fisiológica/fisiologia , Temperatura Baixa , Privação do Sono/fisiopatologia , Adulto , Pressão Sanguínea/fisiologia , Regulação da Temperatura Corporal/fisiologia , Frequência Cardíaca/fisiologia , Humanos , Imersão/fisiopatologia , Masculino , Medição da Dor , Percepção da Dor/fisiologia , Temperatura Cutânea/fisiologia , Fatores de Tempo , Vasodilatação/fisiologia
19.
J Chem Phys ; 135(13): 134313, 2011 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-21992311

RESUMO

Reaction probabilities as a function of total angular momentum (opacity functions) and the resulting reaction cross sections for the collision of open shell S((1)D) atoms with para-hydrogen have been calculated in the kinetic energy range 0.09-10 meV (1-120 K). The quantum mechanical hyperspherical reactive scattering method and quasi-classical trajectory and statistical quasi-classical trajectory approaches were used. Two different ab initio potential energy surfaces (PESs) have been considered. The widely used reproducing kernel Hilbert space (RKHS) PES by Ho et al. [T.-S. Ho, T. Hollebeek, H. Rabitz, S. D. Chao, R. T. Skodje, A. S. Zyubin, and A. M. Mebel, J. Chem. Phys 116, 4124 (2002)] and the recently published accurate double many-body expansion (DMBE)/complete basis set (CBS) PES by Song and Varandas [Y. Z. Song and A. J. C. Varandas, J. Chem. Phys. 130, 134317 (2009)]. The calculations at low collision energies reveal very different dynamical behaviors on the two PESs. The reactivity on the RKHS PES is found to be considerably larger than that on the DMBE/CBS PES as a result of larger reaction probabilities at low total (here also orbital) angular momentum values and to opacity functions which extend to significantly larger total angular momentum values. The observed differences have their origin in two major distinct topographic features. Although both PESs are essentially barrierless for equilibrium H-H distances, when the H-H bond is compressed the DMBE/CBS PES gives rise to a dynamical barrier which limits the reactivity of the system. This barrier is completely absent in the RHKS PES. In addition, the latter PES exhibits a van der Walls well in the entrance channel which reduces the height of the centrifugal barrier and is able to support resonances. As a result, a significant larger cross section is found on this PES, with marked oscillations attributable to shape resonances and/or to the opening of partial wave contributions. The comparison of the results on both PESs is illustrative of the wealth of the dynamics at low collision energy. It is also illuminating about the difficulties encountered in modeling an all-purpose global potential energy surface.

20.
Phys Chem Chem Phys ; 13(18): 8359-70, 2011 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-21373672

RESUMO

Reactive cross-sections for the collision of open shell S((1)D) atoms with ortho- and para-hydrogen, in the kinetic energy range 1-120 K, have been calculated using the hyperspherical quantum reactive scattering method developed by Launay et al. [Chem. Phys. Lett., 1990, 169, 473]. Short-range interactions, described using the ab initio potential energy surface by Ho et al. [J. Chem. Phys., 2002, 116, 4124], were complemented with an accurate description of the long-range interactions, where the main electrostatic (∼R(-5)) and dispersion (∼R(-6)) contributions were considered. This allows the comparison with recent experimental measurements of rate constants and excitation functions for the title reaction at low temperatures [Berteloite et al., Phys. Rev. Lett., 2010, 105, 203201]. The agreement is fairly good. The behavior in the considered energy range can be understood on average in terms of a classical Langevin (capture) model, where the centrifugal barriers determine the amount of reactive flux which reaches the barrierless transition state. Additionally, the structure of the van der Waals well provides temporal trapping at intermediate intermolecular distances thus allowing the system to find its way to the reaction at some classically-forbidden energies. Interestingly, the cross-section for para-hydrogen shows clearly oscillating features associated with the opening of new partial waves and with shape resonances which may be amenable to experimental detection.

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