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Diabetes Mellitus , Saúde Global , Medicina de Precisão , Humanos , Diabetes Mellitus/terapiaRESUMO
OBJECTIVES: To describe the measurement of heart rate turbulence (HRT) after ventricular premature beats and compare HRT in healthy Doberman pinschers and those with dilated cardiomyopathy (DCM), with and without congestive heart failure (CHF). ANIMALS: Sixty-five client-owned Dobermans: 20 healthy (NORMAL), 31 with preclinical DCM and 14 with DCM and CHF (DCM + CHF). METHODS: A retrospective study of data retrieved from clinical records and ambulatory ECG (Holter) archives, including data collected previously for a large-scale prospective study of Dobermans with preclinical DCM. Holter data were reanalysed quantitatively, including conventional time-domain heart rate variability and the HRT parameters turbulence onset and turbulence slope. RESULTS: Heart rate turbulence could be measured in 58/65 dogs. Six Holter recordings had inadequate ventricular premature contractions (VPCs) and one exhibited VPCs too similar to sinus morphology. Heart rate turbulence parameter, turbulence onset, was significantly reduced in DCM dogs, whereas conventional heart rate variability measures were not. Heart rate variability and HRT markers were reduced in DCM + CHF dogs as expected. CONCLUSIONS: Heart rate turbulence can be measured from the majority of good quality standard canine 24-hour Holter recordings with >5 VPCs. Turbulence onset is significantly reduced in Dobermans with preclinical DCM which indicates vagal withdrawal early in the course of disease. Heart rate turbulence is a powerful prognostic indicator in human cardiac disease which can be measured from standard 24-hour ambulatory ECG (Holter) recordings using appropriate computer software. Further studies are warranted to assess whether HRT may be of prognostic value in dogs with preclinical DCM and in other canine cardiac disease.
Assuntos
Cardiomiopatia Dilatada/veterinária , Doenças do Cão/fisiopatologia , Complexos Ventriculares Prematuros/veterinária , Animais , Cardiomiopatia Dilatada/diagnóstico , Cardiomiopatia Dilatada/fisiopatologia , Estudos de Casos e Controles , Doenças do Cão/diagnóstico , Cães , Eletrocardiografia Ambulatorial/veterinária , Feminino , Frequência Cardíaca , Masculino , Linhagem , Estudos Prospectivos , Estudos Retrospectivos , Complexos Ventriculares Prematuros/diagnóstico , Complexos Ventriculares Prematuros/fisiopatologiaRESUMO
After acute myocardial infarction (AMI), neutrophils are recruited to the affected myocardium. Hypochlorous acid (HOCl) produced by neutrophil myeloperoxidase (MPO) damages cardiomyocytes and potentially expands the primary infarct. Rat cardiomyocyte-like cells were incubated with isolated human neutrophils treated with chemical activators in the absence or presence of nitroxide 4-methoxy-Tempo (MetT; 25 µM) for 4, 6 or 24 h; studies with reagent HOCl served as positive control. Treating cardiomyocytes with activated neutrophils or reagent HOCl resulted in a marked increase in protein tyrosine chlorination and a decline in protein tyrosine phosphatase (PTP) activity. On balance our data also supported an increase in phosphorylation of MAPK p38 and ERK1/2 suggestive of an intracellular hyperphosphorylation status and this was accompanied by decreases in cell viability, as judged by assessing caspases-3/7 activity. For cells exposed to activated neutrophils receptor-mediated uptake of transferrin decreased although total matrix metalloproteinase (MMP) activity was unaffected. Addition of MetT ameliorated protein tyrosine chlorination, decreased MAPK activity and restored receptor-mediated transferrin uptake and PTP activity in cardiomyocytes. Overall, adverse effects of neutrophil-derived HOCl on cultured cardiomyocytes were ameliorated by MetT suggesting that nitroxides may be beneficial to inflammatory pathologies, where neutrophil recruitment/activation is a prominent and early feature.
Assuntos
Óxidos N-Cíclicos/farmacologia , Neutrófilos/metabolismo , Proteínas Quinases/metabolismo , Animais , Apoptose/efeitos dos fármacos , Linhagem Celular , Relação Dose-Resposta a Droga , Ativação Enzimática/efeitos dos fármacos , Regulação da Expressão Gênica/efeitos dos fármacos , Humanos , Miócitos Cardíacos/citologia , Miócitos Cardíacos/efeitos dos fármacos , Miócitos Cardíacos/metabolismo , Neutrófilos/enzimologia , Especificidade de Órgãos , Estresse Oxidativo/efeitos dos fármacos , Peroxidase/metabolismo , Monoéster Fosfórico Hidrolases/metabolismo , Fosforilação/efeitos dos fármacos , Transporte Proteico/efeitos dos fármacos , Ratos , Transferrina/metabolismo , Tirosina/metabolismo , Miosinas Ventriculares/genéticaRESUMO
Aqueous-phase reforming of ethylene glycol over alumina-supported Pt-based catalysts is reported. Performance of the catalysts is investigated by conducting kinetics and in situ attenuated total reflectance (ATR)-IR spectroscopic analysis. Pt/γ-Al2 O3 is unstable under APR conditions (270 °C, 90 bar) and undergoes phase transformation to boehmite [AlO(OH)]. This conversion of alumina is studied in situ by using ATR-IR spectroscopy; transition into boehmite proceeds even at milder conditions (210 °C, 40â bar). Pt/γ-Al2 O3 deactivates irreversibly because the Pt surface area decreases owing to an increasing metal particle size and coverage with boehmite. However, Pt supported on boehmite itself shows stable activity. Surprisingly, the rate of formation of hydrogen per Pt surface atom is significantly higher on boehmite compared to an alumina-supported catalyst. This observation seems correlated to both increased concentration of surface OH groups as well as to enhanced oxidation of Pt when comparing Pt/γ-Al2 O3 with Pt/AlO(OH).
Assuntos
Etilenoglicol/química , Hidrogênio/química , Energia Renovável , Água/química , Hidróxido de Alumínio/química , Óxido de Alumínio/química , Catálise , Platina/químicaRESUMO
The objetive of the study was to identify a) the motivations for communicating about non-suicidal self-injury (NSSI) in a publicly accessible online forum, b) The significance (if any) of the "publicness" of the behavior. Using a Thematic Analysis of 423 text-based posts from an online NSSI forum, 5 motivations for using the site were identified: confessional, marking a turning point, acting as a deterrent, dispelling myths and offering or seeking support. Motivations for using the site differ markedly from motivations for engaging in NSSI and tend to be more outwardly focused. The publicness of the site therefore seems to be significant in terms of bearing witness, providing the opportunity to confront negative stereotypes, and the ability to seek and offer support to like-minded individuals.
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Internet/estatística & dados numéricos , Autorrevelação , Comportamento Autodestrutivo/prevenção & controle , Rede Social , Apoio Social , Humanos , Motivação , Comportamento Autodestrutivo/psicologia , Tentativa de Suicídio/prevenção & controle , Inquéritos e QuestionáriosRESUMO
Hexa-ammonium functionalized Dendriphos ligands and mono-sulfonate functionalized metal complexes have been used as building blocks for the preparation of multimetallic dendritic assemblies. These metallodendrimers consist of a single metal centre surrounded by an oligocationic shell formed by the coordinated Dendriphos ligands and multiple associated anionic organometallic complexes.
Assuntos
Técnicas de Química Sintética/métodos , Dendrímeros/química , Dendrímeros/síntese química , Compostos Organometálicos/química , Compostos Organometálicos/síntese química , Ligantes , Compostos de Amônio Quaternário/químicaRESUMO
A method for the Friedel-Crafts-type insertion reaction of acetylene with acid chlorides in chloroaluminate ionic liquids is presented. The use of ionic liquids not only serves to avoid the use of carbon tetrachloride or 1,2-dichloroethane but also suppresses side reactions, notably the polymerization of acetylene, which occurs in these chlorinated solvents. Consequently, the products can be isolated using a simpler purification procedure, giving a range of aromatic and aliphatic ß-chlorovinyl ketones in high yield and purity.
Assuntos
Acetileno/química , Alumínio/química , Cloro/química , Líquidos Iônicos/química , Cetonas/síntese química , Compostos de Vinila/síntese química , Estrutura MolecularRESUMO
The Pt(II) coordination chemistry of oligocationic ammoniomethyl- and neutral aminomethyl-substituted triarylphosphines (L) is described. Complexes of the type PtX(2)(L)(2) (X = Cl, I) have been isolated and characterized. For the hexa-meta-ammoniomethyl-substituted ligands [1](6+) and [2](6+), two ligands always occupy a trans-configuration with respect to each other in complexes of the type PtX(2)(L)(2), while for the tri-para-ammoniomethyl-substituted ligand [7](3+), the trans/cis ratio is dependent on the ionic strength of the solution. This behaviour was not observed for the neutral aminomethyl-substituted ligands. In the crystal structure of trans-[PtI(2)(1)(2)]I(12), the geometrical parameters of the phosphine ligand [1](6+) are very similar to those found in the analogous complex of the benchmark ligand PPh(3), i.e. trans-PtI(2)(PPh(3))(2), indicating that no significant increase in the steric congestion is present in the complex. Instead, the coordination chemistry of this class of phosphine ligands is dominated by repulsive Coulombic inter-ligand interactions.
Assuntos
Fosfinas/química , Platina/química , Cloretos/química , Ligantes , Espectroscopia de Ressonância Magnética , Estrutura Molecular , Espectrometria de Massas por Ionização por ElectrosprayRESUMO
The effects of introducing ionic functionalities in phosphine ligands on the coordination chemistry of these ligands and the catalytic behavior of the corresponding metal complexes are reviewed. The steric and electronic consequences of such functionalizations are discussed. Apart from these steric and electronic effects, the presence of charged groups often leads to additional, supramolecular interactions that occur in the second coordination sphere of the metal complex, such as intramolecular, interligand hydrogen bonding and Coulombic repulsion. These interactions can significantly alter the behavior of the phosphine ligand in question. Such effects have been observed in phosphine-metal association/dissociation equilibria, ligand substitution reactions, and stereoisomerism in phosphine-metal complexes. By drawing general conclusions, this review offers an insight into the coordination and catalytic behavior of phosphine ligands containing ionic functionalities and their corresponding metal complexes.
RESUMO
The combination of Pd(2)dba(3) x CHCl(3) and hexacationic triarylphosphine-based Dendriphos ligands (1-3) leads to a highly active catalytic system in the Suzuki-Miyaura cross-coupling reaction. Under relatively mild reaction conditions, nonactivated aryl bromides and activated aryl chlorides can be coupled at a low Pd loading (0.1 mol %). The observed activity of this catalytic system, in particular in coupling reactions of aryl chlorides, is dramatically higher than that of conventional Pd catalysts employing triarylphosphine ligands. Through control and poisoning experiments, it is concluded that a homogeneous Pd(0)-Dendriphos complex is the active species in this catalytic system. Despite their triarylphosphine-based structure, Dendriphos ligands behave as very bulky phosphine ligands and lead to a preferential formation of coordinatively unsaturated and catalytically active Pd(0) species, which explains the observed high catalytic activity for these systems. The presence of six permanent cationic charges in the backbone of this class of ligands is proposed to result in a significant interligand Coulombic repulsion and plays a crucial role in their bulky behavior. In the coupling reactions of activated aryl chlorides, a positive dendritic kinetic effect was observed among the different Dendriphos generations, indicating an increased ability of the higher ligand generations to stabilize the active species due to steric effects. For aryl bromides, no dendritic effect was observed due to a shift in the rate-determining step in the catalytic cycle, from oxidative addition for aryl chlorides to transmetalation for aryl bromides.
RESUMO
This work reviews recent developments in the field of organic transformations on sigma-aryl organometallic complexes. The general notion that M--C sigma bonds are kinetically labile, highly reactive, and incompatible with typical reaction conditions met in organic synthesis has limited the use of these synthetic strategies thus far. However, organic transformations on metal-bound sigma-aryl fragments are being used more and more by chemists in both industry and academia. In this Review, emphasis is put on the synthetic methods applied in this field up to now. The simplicity and generally good yields of these methods are very attractive for the construction of functionalized organometallic building blocks that are potentially useful as photochemical molecular devices, biosensors and -conjugates, or molecular switches. Thus, this Review has been tailored for a broader audience with the aim of encouraging the application of these strategies.
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The synthesis of two organogold(I) complexes, [(Au(NCN))2(dppbp)] (6) and [(Au(Phebox))2(dppbp)] (9), and their application in subsequent transmetalating reactions are described. A trinuclear organogold(I) complex, [(AuCl)3(tdpppb)] (4) is also reported, which exhibits a surprisingly high solubility in dichloromethane. It was found that 6 and 9 can cleanly transfer the anionic NCN-([C(6)H(3)(CH(2)NMe(2))2-2,6]-) or Phebox-([2,6-bis(oxazolinyl)phenyl]-) moiety to Ti(IV) and Pd(II) centers, respectively. The coproduct [(AuCl)2(dppbp)] (3, dppbp is [4-Ph(2)PC(6)H(4)]2 (1)) formed during this transmetalation reaction, precipitates almost quantitatively from the reaction mixture (toluene) and can thus be separated by simple filtration. In comparison, [AuCl(PPh3)], formed as the coproduct in the transmetalation reaction of [Au(NCN)(PPh3)] with metal salts, has a higher solubility in apolar solvents and thus is more difficult to separate from the resultant organometallic complex. Digold complex 6 has been characterized by NMR spectroscopy and crystallographic analyses. These analyses show that the two gold units are essentially independent. The formation of a dimetallic transmetalating agent based on gold(I) had no effect on its transmetalating properties.
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We previously reported that broilers fed n-methyl-D,L-aspartate (NMA) exhibited enhanced feed conversion efficiency and decreased percentage of fat in carcasses. In this experiment, growth performance and backfat thickness were evaluated in barrows fed NMA. Poland China x Yorkshire barrows weighing 68.8 +/- 1.7 kg (mean +/- SE) were allowed ad libitum access to feed containing NMA at levels of either 0 (n = 7), 100 (n = 6), 200 (n = 8), or 300 (n = 8) mg/kg for 36 d. Barrows were slaughtered at 99.5 +/- 2.3 kg BW. There was no effect (P > 0.1) of NMA on ADG or feed consumption. Gain:feed ratio decreased (P < 0.03) in a linear fashion with increasing level of NMA. There was a cubic effect (P < 0.05) of NMA treatment on first-rib backfat thickness. In response to graded levels of NMA, backfat thickness at the 10th rib (P < 0.08) and last rib (P < 0.03) increased in a linear fashion. The NMA had no effect (P > 0.1) on backfat thickness measured at the lumbar vertebra or longissimus muscle area measured at the 10th rib interface. The percentage of lean in the carcass decreased in a linear fashion (P < 0.05) in response to increasing levels of NMA in the diet. In summary, NMA had an overall negative effect on growth performance and carcass yield characteristics in barrows. The dichotomous effects of NMA on feed efficiency and body composition in poultry and swine warrants further scrutiny.
Assuntos
Tecido Adiposo/anatomia & histologia , N-Metilaspartato/farmacologia , Suínos/anatomia & histologia , Tecido Adiposo/efeitos dos fármacos , Animais , Composição Corporal/efeitos dos fármacos , Peso Corporal , Ingestão de Alimentos , Ingestão de Energia , Metabolismo Energético , Músculos/efeitos dos fármacos , Suínos/crescimento & desenvolvimentoRESUMO
A closed household of 26 cats in which feline coronavirus (FCoV), feline leukaemia virus (FeLV) and feline immunodeficiency virus (FIV) were endemic was observed for 10 years. Each cat was seropositive for FCoV on at least one occasion and the infection was maintained by reinfection. After 10 years, three of six surviving cats were still seropositive. Only one cat, which was also infected with FIV, developed feline infectious peritonitis (FIP). Rising anti-FCoV antibody titres did not indicate that the cat would develop FIP. The FeLV infection was self-limiting because all seven of the initially viraemic cats died within five years and the remainder were immune. However, FeLV had the greatest impact on mortality. Nine cats were initially FIV-positive and six more cats became infected during the course of the study, without evidence of having been bitten. The FIV infection did not adversely affect the cats' life expectancy.
Assuntos
Infecções por Coronavirus/veterinária , Síndrome de Imunodeficiência Adquirida Felina/transmissão , Vírus da Imunodeficiência Felina/isolamento & purificação , Vírus da Leucemia Felina/isolamento & purificação , Leucemia Felina/transmissão , Animais , Anticorpos Antivirais/isolamento & purificação , Gatos , Causas de Morte , Coronavirus/isolamento & purificação , Infecções por Coronavirus/mortalidade , Infecções por Coronavirus/transmissão , Ensaio de Imunoadsorção Enzimática , Síndrome de Imunodeficiência Adquirida Felina/mortalidade , Peritonite Infecciosa Felina/transmissão , Feminino , Abrigo para Animais , Leucemia Felina/mortalidade , Expectativa de Vida , MasculinoRESUMO
This multisite investigation assessed subjective, behavioral, and objective balance function in 30 blast survivors. Subjects with vertigo, dizziness, or imbalance were screened (n = 6) or evaluated (n = 27) during 1 year. Tests included a questionnaire, electronystagmography (ENG), and computerized dynamic posturography (CDP). Ninety-seven percent of subjects were located inside a building during the blast, and 63 percent of subjects experienced dysequilibrium within 48 hours. Forty-three percent of symptoms could not be attributed to head injury. Sixty percent of subjects had abnormal ENG and/or CDP; ENG abnormalities mostly were peripheral or nonlocalizing, whereas CDP patterns were "vestibular," "surface dependent," and "physiologically inconsistent." At 1-year postblast, 55 percent of initially abnormal CDP results were normal, and 72 percent of subjects said symptoms were unchanged or occurred intermittently. A serial, test battery approach is recommended to assess symptoms. Blast-related dysequilibrium had clinically significant manifestations and should be considered a valid component of aural blast injury.
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Sobreviventes/psicologia , Doenças Vestibulares/diagnóstico , Adulto , Testes Calóricos , Tontura/diagnóstico , Tontura/etiologia , Eletronistagmografia , Feminino , Perda Auditiva Provocada por Ruído/complicações , Perda Auditiva Neurossensorial/diagnóstico , Perda Auditiva Neurossensorial/etiologia , Humanos , Masculino , Pessoa de Meia-Idade , Oklahoma , Postura , Inquéritos e Questionários , Doenças Vestibulares/etiologia , Testes de Função VestibularRESUMO
Early respiratory disease complex (ERDC) is a term coined to describe an acute disease characterized by depression, respiratory distress, and increased mortality in 2-to-3-wk-old broiler chickens. Postmortem lesions include airsacculitis, fibrinous pericarditis, and perihepatitis. Colisepticemia is the primary cause of death. In order to investigate the association between ERDC and farm management factors, a retrospective case-control study was conducted by collecting data covering a 6-mo period (January-June 1997) from four broiler integrators on the Delmarva peninsula. Univariate and multivariate statistical analyses revealed that flock size was positively associated (P = 0.02) and layout time was negatively associated (P = 0.05) with ERDC.
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Criação de Animais Domésticos , Doenças das Aves Domésticas/epidemiologia , Doenças Respiratórias/veterinária , Doença Aguda , Animais , Estudos de Casos e Controles , Galinhas , Delaware/epidemiologia , Feminino , Masculino , Maryland/epidemiologia , Análise Multivariada , Doenças Respiratórias/epidemiologia , Estudos Retrospectivos , Fatores de Risco , Virginia/epidemiologiaRESUMO
This longitudinal study evaluated subjective, behavioral, and objective auditory function in 83 explosion survivors. Subjects were evaluated quarterly for 1 year with conventional pure-tone and extended high-frequencies audiometry, otoscopic inspections, immittance and speech audiometry, and questionnaires. There was no obvious relationship between subject location and symptoms or test results. Tinnitus, distorted hearing, loudness sensitivity, and otalgia were common symptoms. On average, 76 percent of subjects had predominantly sensorineural hearing loss at one or more frequencies. Twenty-four percent of subjects required amplification. Extended high frequencies showed evidence of acoustic trauma even when conventional frequencies fell within the normal range. Males had significantly poorer responses than females across frequencies. Auditory status of the group was significantly compromised and unchanged at the end of 1-year postblast.
Assuntos
Explosões , Perda Auditiva Provocada por Ruído/complicações , Perda Auditiva Neurossensorial/diagnóstico , Perda Auditiva Neurossensorial/etiologia , Zumbido/diagnóstico , Zumbido/etiologia , Violência , Adolescente , Adulto , Idoso , Audiometria de Tons Puros , Audiometria da Fala , Criança , Pré-Escolar , Feminino , Seguimentos , Auxiliares de Audição , Perda Auditiva Neurossensorial/terapia , Humanos , Masculino , Pessoa de Meia-Idade , Oklahoma , Fatores Sexuais , Inquéritos e Questionários , Fatores de TempoRESUMO
OBJECTIVE: To study the effectiveness of a 1990 ban by New York state on entry to more than one waiting list for a cadaver kidney transplant, and the impact of the ban on equity in access to transplantation. DATA SOURCES: (1) Waiting list files from the Organ Procurement and Transplantation Network, (2) the Health Care Financing Administration's Medicare Program Management and Medical Information System, and (3) U.S. Census Public Use Files. STUDY DESIGN: Multivariate hazard models were used to estimate the impact of the ban of the overall odds of multiple listing and on the odds of multiple listing at in-state and out-of-state transplant centers. After estimating the relationship between multiple listing and subsequent transplantation, we used simulation techniques to estimate the effects of a complete multiple listing ban on group waiting time differentials. Independent variables included demographic/socioeconomic characteristics, measures of ESRD severity, general transplantation suitability, measures that affect the likelihood of finding a good donor organ, and measures of the productivity of the transplant/dialysis center. PRINCIPAL FINDINGS: The ban was associated with a 66 percent reduction in the rate of multiple listing for New York patients, and multiple listing at in-state transplant centers declined by 87 percent. Simulation results suggested that even a completely effective ban would produce only small, mixed equity effects. CONCLUSIONS: While the ban was effective in reducing the proportion of patients who registered at multiple transplant centers, taken together the results suggest that banning multiple listing is not likely to result in large improvements in equity in access to transplantation.