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1.
Phys Chem Chem Phys ; 26(28): 19138-19160, 2024 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-38962964

RESUMO

Plasmonic metal nanoclusters are widely used in chemistry, nanotechnology, and biomedicine. In metal nanocluster dimers, coupling of the plasmons leads to the emergence of two distinct types of modes: (1) bonding dipole plasmons (BDP), which occurs when charge oscillates synchronously within each nanocluster, and (2) charge transfer plasmons (CTP), which occurs when charge oscillates between two conductively linked nanoclusters. Although TDDFT-based modeling has uncovered some trends in these modes, it is computationally expensive for large dimers, and quantitative analysis is challenging. Here, we demonstrate that the semiempirical quantum mechanical method INDO/CIS enables us to quantify the CTP character of each excited state efficiently. In end-to-end Ag nanowire dimers, the longitudinal states have CTP character that decreases with increasing gap distance and nanowire length. In side-by-side dimers, the transverse states have CTP character and generally larger than in the end-to-end dimers, particularly for the longer nanowires. In side-by-side dimers where one nanowire is shifted along the length of the other, the CTP character of the longitudinal states peaks when the dimer is shifted by two Ag-Ag bond lengths, while the transverse states show decreasing CTP character as displacement increases. In the larger Ag31+ nanorod dimers, CTP character follow a similar distance dependence to that seen in the small nanowire but have smaller overall CTP character than the nanowires. Our study demonstrates that INDO/CIS is capable of modeling metal nanocluster dimers at a low computational cost, making it possible to study larger dimers that are difficult to analyze using TDDFT.

2.
Niger J Clin Pract ; 27(1): 62-67, 2024 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-38317036

RESUMO

BACKGROUND: The coronavirus disease 2019 (COVID-19) pandemic has led to a significant increase in global mortality rates. Numerous studies have been conducted to identify the factors associated with mortality in COVID-19 cases. In these studies, overall mortality was evaluated in patients, and no distinction was made as ward or intensive care mortality. AIM: This study aims to determine mortality-related factors in patients who died while in the ward. This could enable us to review the indications for intensive care hospitalization in possible pandemics. MATERIALS AND METHOD: This retrospective study was conducted on a cohort of 237 patients who applied to our institution between January 2020 and December 2021 with the diagnosis of COVID-19. Demographic characteristics, length of stay, type of admission (emergency ward or outpatient clinic), presence of comorbidities, thoracic computerized tomography (CT) findings, and laboratory findings were extracted from the hospital database. The demographic and laboratory results of both deceased and recovered patients were compared. RESULTS: While many demographic and laboratory findings were statistically significant in the initial analysis, multiple logistic regression analysis showed that decreased albumin levels (adjusted OR = 0.23, 95% CI = 0.09 - 0.57), increased troponin (adjusted OR = 1.03, 95% CI = 1.02 - 1.05), and procalcitonin (adjusted OR = 3.46, 95% CI = 1.04 - 11.47) levels and higher partial thromboplastin time (PTT) (adjusted OR = 1.18, 95% CI = 1.09 - 1.28) values, presence of diabetes mellitus (DM) in patients (adjusted OR = 2.18, 95% CI = 1.01 - 4.69, P = 0.047), and admission to hospital from the emergency department (adjusted OR = 5.15, 95% CI = 1.45 - 18.27, P = 0.011) were significantly associated with mortality when adjusted for age. When a predictive model is constructed with these variables, this model predicted mortality statistically significant (AUC = 0.904, 95% CI = 0.856 - 0.938, P < 0.001), with a sensitivity of 77.2% (95% CI, 67.8 - 85), a specificity of 91.2% (95% CI, 85.1 - 95.4), a positive predictive value (PPV) of 86.7% (95% CI, 72 - 85.3), and an negative predictive value (NPV) of 84.4% (95% CI, 79.4 - 89.6). CONCLUSION: In this study, we may predict mortality among COVID-19-diagnosed patients admitted to the ward via this model which has the potential to provide guidance for reconsidering the indications for intensive care unit (ICU) admission.


Assuntos
COVID-19 , Humanos , Estudos Retrospectivos , SARS-CoV-2 , Hospitalização , Comorbidade , Unidades de Terapia Intensiva , Mortalidade Hospitalar
3.
Int Arch Allergy Immunol ; 184(2): 142-148, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36327939

RESUMO

INTRODUCTION: Awareness of risk factors for asthma exacerbation can reduce the morbidity and mortality of the disease. The current study aimed to investigate the risk factors associated with current asthma exacerbations in school-age children. METHODS: This study enrolled children who were admitted to a tertiary outpatient paediatric allergy and asthma department and were diagnosed with asthma. Patients and their caregivers underwent an interviewer-administered questionnaire, which obtained information regarding the demographic features and parameters to determine environmental exposures along with previous disease history. Laboratory examinations, including complete blood count with differential, total IgE levels, skin prick tests, and pulmonary function tests, were also performed. RESULTS: A total of 431 children (288 male, 66.8%) with a median age (interquartile range) of 8.1 (6.3-11.2) years were included, among whom 265 (61.5%) had aeroallergen sensitization. Asthma was controlled, partially controlled, and uncontrolled in 154 (35.7%), 53 (12.3%), and 143 (33.2%) patients, respectively. A total of 81 patients (18.8%) experienced asthma exacerbation. Multivariate logistic regression analysis revealed that a history of asthma exacerbation within the last year (odds ratio [confidence interval]) (20.73 [9.95-43.20]; p < 0.001), a shorter asthma duration (<2.5 years) (2.58 [1.44-4.61]; p = 0.001), and a lack of regular controller therapy (4.12 [1.54-10.98]; p = 0.005) were associated with current asthma exacerbation. DISCUSSION/CONCLUSION: Awareness of risk factors for asthma exacerbation may help physicians treat school-age children with asthma by providing prompt and rational interventions in order to prevent asthma exacerbations.


Assuntos
Asma , Hipersensibilidade , Humanos , Criança , Masculino , Progressão da Doença , Asma/diagnóstico , Asma/epidemiologia , Hospitalização , Fatores de Risco
4.
Microb Cell Fact ; 22(1): 108, 2023 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-37280676

RESUMO

With the dramatic decrease in fossil fuel stocks and their detrimental effects on the environment, renewable energy sources have gained imminent importance in the mitigation of emissions. As lipid-enriched energy stocks, cyanobacteria are the leading group of microorganisms contributing to the advent of a new energy era. In the present study, the impact of Nanofer 25 s nanoscale zero-valent iron nanoparticles (nZVIs) and ampicillin on lipid production and cellular structural changes in Fremyella diplosiphon strain B481-SD were investigated. Total lipid abundance, fatty acid methyl ester (FAME) compositions, and alkene production as detected by high-resolution two-dimensional gas chromatography with time-of-flight mass spectrometry (GC × GC/TOF-MS) was significantly higher (p < 0.05) in the individual application of 0.8 mg/L ampicillin, 3.2 mg/L nZVIs, and a combined regimen of 0.8 mg/L ampicillin and 3.2 mg/L nZVIs compared to the untreated control. In addition, we identified significant increases (p < 0.05) in monounsaturated fatty acids (MUFAs) in F. diplosiphon treated with the combination regimen compared to the untreated control, 0.8 mg/L of ampicillin, and 3.2 mg/L of nZVIs. Furthermore, individual treatment with 0.8 mg/L ampicillin and the combination regimen (0.8 mg/L ampicillin + 3.2 mg/L nZVIs) significantly increased (p < 0.05) Nile red fluorescence compared to the untreated control, indicating neutral membrane lipids to be the main target of ampicillin added treatments. Transmission electron microscopy studies revealed the presence of single-layered thylakoid membranes in the untreated control, while complex stacked membranes of 5-8 layers were visualized in ampicillin and nZVI-treated F. diplosiphon. Our results indicate that nZVIs in combination with ampicillin significantly enhanced total lipids, essential FAMEs, and alkenes in F. diplosiphon. These findings offer a promising approach to augment the potential of using the strain as a large-scale biofuel agent.


Assuntos
Cianobactérias , Nanopartículas , Ferro/química , Ácidos Graxos
5.
Nature ; 550(7676): 407-410, 2017 10 19.
Artigo em Inglês | MEDLINE | ID: mdl-28931002

RESUMO

The RNA-guided CRISPR-Cas9 nuclease from Streptococcus pyogenes (SpCas9) has been widely repurposed for genome editing. High-fidelity (SpCas9-HF1) and enhanced specificity (eSpCas9(1.1)) variants exhibit substantially reduced off-target cleavage in human cells, but the mechanism of target discrimination and the potential to further improve fidelity are unknown. Here, using single-molecule Förster resonance energy transfer experiments, we show that both SpCas9-HF1 and eSpCas9(1.1) are trapped in an inactive state when bound to mismatched targets. We find that a non-catalytic domain within Cas9, REC3, recognizes target complementarity and governs the HNH nuclease to regulate overall catalytic competence. Exploiting this observation, we design a new hyper-accurate Cas9 variant (HypaCas9) that demonstrates high genome-wide specificity without compromising on-target activity in human cells. These results offer a more comprehensive model to rationalize and modify the balance between target recognition and nuclease activation for precision genome editing.


Assuntos
Proteínas Associadas a CRISPR/química , Proteínas Associadas a CRISPR/metabolismo , Sistemas CRISPR-Cas , Edição de Genes/métodos , Mutagênese , Streptococcus pyogenes/enzimologia , Biotecnologia/métodos , Proteínas Associadas a CRISPR/genética , Endonucleases/química , Endonucleases/genética , Endonucleases/metabolismo , Ativação Enzimática , Variação Genética , Humanos , Domínios Proteicos , Streptococcus pyogenes/genética , Especificidade por Substrato
6.
Int Arch Allergy Immunol ; 183(5): 517-525, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-34903689

RESUMO

BACKGROUND: Asthma diagnosis may be challenging particularly in patients with mild symptoms without an obstructive pattern in spirometry. Detection of airway hyperresponsiveness (AHR) by a positive methacholine challenge (MCC) is still an important diagnostic tool to confirm the presence of asthma with reasonable certainty. However, it is time consuming and could be exhausting for patients. We aimed to identify the predictive factors for AHR in children with respiratory symptoms without obstructive pattern in spirometry. METHODS: Data from children who had undergone MCC were analyzed retrospectively. The demographic features of patients along with laboratory results were collected. RESULTS: A total of 123 children with a median age of 10.5 years were enrolled. AHR was detected in 81 children (65.8%). The age of the children with AHR was significantly younger. The prevalences of aeroallergen sensitization, nocturnal cough, wheezing, and a baseline forced expiratory flow at 75% of vital capacity (FEF75) <65% were significantly more frequent in children with AHR. Multivariate logistic regression analysis revealed age, ever wheezing, nocturnal cough, tree pollen allergy, and FEF75 <65% as independent predictors of AHR. A weighted clinical risk score was developed (range, 0-75 points). At a cutoff point of 35, the presence of AHR is predicted with a specificity of 90.5% and a positive predictive value of 91.5%. CONCLUSION: In children suspected of having asthma, but without an obstructive pattern in the spirometry, combining independent predictors, which can be easily obtained in clinical practice, might be used to identify children with AHR.


Assuntos
Asma , Hiper-Reatividade Brônquica , Hipersensibilidade Respiratória , Asma/diagnóstico , Asma/epidemiologia , Hiper-Reatividade Brônquica/diagnóstico , Hiper-Reatividade Brônquica/epidemiologia , Testes de Provocação Brônquica , Criança , Tosse , Volume Expiratório Forçado , Humanos , Cloreto de Metacolina , Sons Respiratórios , Estudos Retrospectivos , Espirometria
7.
Pediatr Surg Int ; 38(12): 1919-1924, 2022 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-36138322

RESUMO

PURPOSE: Minimally invasive pectus excavatum repair has gained widespread acceptance and its results and complications are well-described. However, there is a substantial debate on the risks and frequencies of complications following metal bar removal. We, therefore, aimed to analyse all complications that occurred during and after metal bar removal at our two paediatric surgical centres. METHODS: Bar removal surgeries were identified via procedural codes and electronic records were reviewed using a pre-specified data extraction chart. Both intra- and postoperative complications were included and the latter scored according to Clavien-Dindo. We analysed the influence of the pre-specified potential predictors age, sex, and the number of implanted metal bars on the occurrence of complications using logistic regression. RESULTS: We included 279 patients with a median age of 19 years (interquartile range 17-20 years). 15 patients experienced 17 complications. Of 11 postoperative complications, only an enlarging pleural effusion required a chest drain in local anaesthesia, resulting in a Claven-Dindo grade IIIa, whereas the remainder were classified as grade I. Neither age (adjusted odds ratio (aOR) 0.97, 95% confidence interval (CI) 0.84-1.13, P = 0.73), nor sex (aOR 0.88, 95% CI 0.19-4.07, P = 0.87) or the number of bars (aOR 0.64, 95% CI 0.15-2.71, P = 0.547) did influence the occurrence of complications. CONCLUSION: Complications following metal bar removal were scarce in our duocentric retrospective series and usually of minor relevance. However, to address the perceived paucity of data on the frequency and severity of complications following metal bar removal, further studies, including large database research is necessary.


Assuntos
Tórax em Funil , Criança , Humanos , Adolescente , Adulto Jovem , Adulto , Estudos Retrospectivos , Tórax em Funil/cirurgia , Próteses e Implantes , Procedimentos Cirúrgicos Minimamente Invasivos/métodos , Complicações Pós-Operatórias/epidemiologia , Complicações Pós-Operatórias/etiologia , Resultado do Tratamento
8.
Phys Chem Chem Phys ; 23(32): 17287-17299, 2021 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-34346427

RESUMO

Ligands dramatically affect the electronic structure of gold nanoclusters (NCs) and provide a useful handle to tune the properties required for nanomaterials that have high performance for important functions like catalysis. Recently, questions have arisen about the nature of the interactions of hydride and halide ligands with Au NCs: hydride and halide ligands have similar effects on the absorption spectra of Au9 NCs, which suggested that the interactions of the two classes of ligands with the Au core may be similar. Here, we elucidate the interactions of halide and hydride ligands with phosphine-protected gold clusters via theoretical investigations. The computed absorption spectra using time-dependent density functional theory are in reasonable agreement with the experimental spectra, confirming that the computational methods are capturing the ligand-metal interactions accurately. Despite the similarities in the absorption spectra, the hydride and halide ligands have distinct geometric and electronic effects. The hydride ligand behaves as a metal dopant and contributes its two electrons to the number of superatomic electrons, while the halides act as electron-withdrawing ligands and do not change the number of superatomic electrons. Clarifying the binding modes of these ligands will aid in future efforts to use ligand derivatization as a powerful tool to rationally design Au NCs for use in functional materials.

9.
J Phys Chem A ; 123(4): 958-965, 2019 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-30615443

RESUMO

Anti-Markovnikov addition of water to olefins has been a long-standing goal in catalysis. The [Rh(COD)(DPEphos)]+ complex was found as a general and regioselective group 9 catalyst for intermolecular hydroamination of alkenes. The reaction mechanism was adapted for intermolecular hydration of alkenes catalyzed by a [Rh(DPEphos)]+ catalyst and studied by DFT calculations. Olefin hydration pathways were analyzed for anti-Markovnikov and Markovnikov regioselectivity. On the basis of the DFT results, the operating mechanism can be summarized as follows: styrene activation through nucleophilic attack by OHδ- of water to alkene with simultaneous Hδ+ transfer to the Rh; this is then followed by formation of primary alcohol via reductive elimination. The competitive formation of phenylethane was studied via a ß-elimination pathway followed by hydrogenation. The origin of the regioselectivity (Markovnikov vs anti-Markovnikov) was analyzed by means of studying the molecular orbitals, plus natural atomic charges, and shown to be primarily orbital-driven rather than charge-driven.

10.
Allergy Asthma Proc ; 39(3): 1-7, 2018 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-29669659

RESUMO

BACKGROUND: Results of epidemiologic studies have determined several risk factors for asthma in school-age children. OBJECTIVE: To examine whether parental and perinatal risk factors, along with infantile feeding patterns, were associated with asthma in children with grass pollen allergy and allergic rhinitis. METHODS: We retrospectively analyzed the data of our cohort, which consisted of children with allergic rhinitis. Only children with grass pollen sensitization were enrolled. A detailed questionnaire regarding demographic features and perinatal events was given to the parents. RESULTS: A total of 293 children (200 boys [68.3%]; with median age, 10.2 years [interquartile range {IQR}, 7.4-13.0 years]) were included. A total of 109 children (37.2%) had accompanying asthma. The median age of onset of rhinitis symptoms was earlier (5.3 years [IQR, 4.0-8.0 years] versus 7.0 years [IQR, 5.0-10.0 years]; p = 0.001), histories of prematurity (16.7 versus 6.5%; p = 0.006), preeclampsia (5.5 versus 0%; p = 0.001), neonatal intensive care unit admission (15.1 versus 6.0%; p = 0.01), phototherapy (17.9 versus 7.1%; p = 0.004), early formula feeding (58.7 versus 41.2%; p = 0.006), and parental asthma (25.0 versus 11.4%; p = 0.002) were more frequent in children with asthma. Multivariate logistic regression analysis revealed prematurity (odds ratio [OR] 2.78 [95% confidence interval [CI],1.24-6.24]; p = 0.013), history of formula feeding (OR 1.81 [95% CI, 1.09-3.01]; p = 0.022), and parental asthma (OR 2.37 [95% CI, 1.22-4.63]; p = 0.011) were associated with asthma in school-age children with grass pollen-induced allergic rhinitis. CONCLUSION: Close monitoring of patients with these risk factors may help with an earlier diagnosis of asthma and prompt initiation of therapeutic interventions in children with allergic rhinitis and who were sensitized to grass pollen.


Assuntos
Asma/epidemiologia , Nascimento Prematuro/epidemiologia , Efeitos Tardios da Exposição Pré-Natal/epidemiologia , Rinite Alérgica Sazonal/epidemiologia , Rinite Alérgica/epidemiologia , Adolescente , Idade de Início , Alérgenos/imunologia , Antígenos de Plantas/imunologia , Criança , Feminino , Humanos , Imunização , Masculino , Pólen/imunologia , Gravidez , Estudos Retrospectivos , Fatores de Risco
11.
Bratisl Lek Listy ; 119(6): 335-340, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-29947232

RESUMO

OBJECTIVE: The aim of this study was to evaluate the relationship between red blood cell distribution width (RDW) and mean platelet volume (MPV) with development of postoperative atrial fibrillation (PoAF) after off-pump coronary artery bypass grafting (CABG). BACKGROUND: The RDW and MPV have been associated with some cardiovascular disorders. METHODS: A total of 93 patients who underwent off-pump CABG were included in this study. The patients were divided into two groups as developing and nondeveloping PoAF groups in the postoperative period. We measured whether RDW and MPV levels are a predictive value for development PoAF. RESULTS: There were 24 patients with PoAF enrolled (mean age: 66 ± 7.8 years) and 69 patients without PoAF (mean age: 56.26 ± 11.53 years). The PoAF was significantly correlated with age (p = 0.004), hematocrit (p: 0.010), RDW (p = 0.007) and creatinine (p = 0.006). Only advanced age (p = 0.012) was identified as an independent predictor of PoAF. For predicting PoAF, there was 79.2 % sensitivity and 65.2 % specificity for RDW (p = 0.001) and 62.5 % sensitivity and 55.1 % specificity for MPV (p = 0.062). CONCLUSIONS: We found that RDW levels and MPV were not an independent predictor of the development of PoAF. However, elevated RDW levels and MPV may be one of the predictive values for PoAF development (Tab. 3, Fig. 2, Ref. 27).


Assuntos
Ponte de Artéria Coronária sem Circulação Extracorpórea , Índices de Eritrócitos , Volume Plaquetário Médio , Complicações Pós-Operatórias/fisiopatologia , Idoso , Fibrilação Atrial/fisiopatologia , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Fatores de Risco , Estatística como Assunto
12.
Niger J Clin Pract ; 21(1): 22-26, 2018 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-29411718

RESUMO

PURPOSE: In chronic hemodialysis patients, the low flow of vascular access may leads to inadequate dialysis, increased rate of hospitalization, morbidity, and mortality. It was found that surveillance should be performed for native arteriovenous (AV) should not be performed for AV graft in various studies. However, surveillance was done in graft AV fistulas in most studies. Doppler ultrasonography (US) was suggested for surveillance of AV fistulas by the last vascular access guideline of National Kidney Foundation Disease Outcomes Quality Initiative (NKF KDOQI). The aim of study is to determine whether glucose pump test (GPT) is used for surveillance of native AV fistulas by using Doppler US as reference. METHODS: In 93 chronic hemodialysis patients with native AV fistula, blood flow rates were measured by Doppler US and GPT. For GPT, glucose was infused to 16 mL/min by pump and was measured at basal before the infusion and 11 s after the start of the infusion by glucometer. Doppler US was done by an expert radiologist. Used statistical tests were Mann-Whitney U test, Friedman test, regression analysis, and multiple regression analysis. RESULTS: Median values of blood flow rates measured by GPT (707 mL/min) and by Doppler US (700 mL/min) were not different (Z = 0.414, P = 0.678). Results of GPT and Doppler US measurements were positive correlate by regression analysis. The mean GPT value of diabetic patients (n = 39; 908 mL/min) was similar to that of nondiabetic patients (n = 54; 751 mL/min; Z = 1.31, P = 0.188). GPT values measured at three different dialysis session did not differ from each other that by Friedman test (F = 0.92, P = 0.39). This showed that GPT was stable and reliable. CONCLUSIONS: Glucose pump test can be used to measure blood flow rate of native AV fistula. GPT is an accurate and reliable test.


Assuntos
Derivação Arteriovenosa Cirúrgica , Glicemia/análise , Adulto , Idoso , Velocidade do Fluxo Sanguíneo , Cateteres de Demora , Feminino , Glucose/administração & dosagem , Humanos , Falência Renal Crônica/fisiopatologia , Falência Renal Crônica/terapia , Masculino , Pessoa de Meia-Idade , Diálise Renal , Reprodutibilidade dos Testes , Ultrassonografia Doppler
13.
J Am Chem Soc ; 139(40): 14292-14301, 2017 10 11.
Artigo em Inglês | MEDLINE | ID: mdl-28956899

RESUMO

Iron(0) pentacarbonyl is an organometallic compound with a long history. It undergoes carbonyl displacement chemistry with various donors (L), leading to molecules of the type Fe(CO)x(L)5-x. The work reported here illustrates that Fe(CO)5 can also act as a ligand. The reaction between Fe(CO)5 with the silver salts AgSbF6 and Ag[B{3,5-(CF3)2C6H3}4] under appropriate conditions resulted in the formation of [(µ-H2O)AgFe(CO)5]2[SbF6]2 and [B{3,5-(CF3)2C6H3}4]AgFe(CO)5, respectively, featuring heterobimetallic {Ag-Fe(CO)5}+ fragments. The treatment of [B{3,5-(CF3)2C6H3}4]AgFe(CO)5 with 4,4'-dimethyl-2,2'-bipyridine (Me2Bipy) and Fe(CO)5 afforded a heterobimetallic [(Me2Bipy)AgFe(CO)5][B{3,5-(CF3)2C6H3}4] species with a Ag-Fe(CO)5 bond and a heterotrimetallic [{Fe(CO)5}2(µ-Ag)][B{3,5-(CF3)2C6H3}4] with a (CO)5Fe-Ag-Fe(CO)5 core, respectively, illustrating that it is possible to manipulate the coordination sphere at silver while keeping the Ag-Fe bond intact. The chemistry of [B{3,5-(CF3)2C6H3}4]AgFe(CO)5 with Et2O and PMes3 (Mes = 2,4,6-trimethylphenyl) has also been investigated, which led to [(Et2O)3Ag][B{3,5-(CF3)2C6H3}4] and [(Mes3P)2Ag][B{3,5-(CF3)2C6H3}4] with the displacement of the Fe(CO)5 ligand. X-ray structural and spectroscopic data of new molecules as well as results of computational analyses are presented. The Fe-Ag bond distances of these metal-only Lewis pairs range from 2.5833(4) to 2.6219(5) Å. These Ag-Fe bonds are of primarily an ionic/electrostatic nature with a modest amount of charge transfer between Ag+ and Fe(CO)5. The ν̅(CO) bands of the molecules with Ag-Fe(CO)5 bonds show a notable blue shift relative to those observed for free Fe(CO)5, indicating a significant reduction in Fe→CO back-bonding upon its coordination to silver(I).

14.
Ann Rheum Dis ; 76(3): 476-485, 2017 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-27457513

RESUMO

OBJECTIVES: Develop recommendations for women's health issues and family planning in systemic lupus erythematosus (SLE) and/or antiphospholipid syndrome (APS). METHODS: Systematic review of evidence followed by modified Delphi method to compile questions, elicit expert opinions and reach consensus. RESULTS: Family planning should be discussed as early as possible after diagnosis. Most women can have successful pregnancies and measures can be taken to reduce the risks of adverse maternal or fetal outcomes. Risk stratification includes disease activity, autoantibody profile, previous vascular and pregnancy morbidity, hypertension and the use of drugs (emphasis on benefits from hydroxychloroquine and antiplatelets/anticoagulants). Hormonal contraception and menopause replacement therapy can be used in patients with stable/inactive disease and low risk of thrombosis. Fertility preservation with gonadotropin-releasing hormone analogues should be considered prior to the use of alkylating agents. Assisted reproduction techniques can be safely used in patients with stable/inactive disease; patients with positive antiphospholipid antibodies/APS should receive anticoagulation and/or low-dose aspirin. Assessment of disease activity, renal function and serological markers is important for diagnosing disease flares and monitoring for obstetrical adverse outcomes. Fetal monitoring includes Doppler ultrasonography and fetal biometry, particularly in the third trimester, to screen for placental insufficiency and small for gestational age fetuses. Screening for gynaecological malignancies is similar to the general population, with increased vigilance for cervical premalignant lesions if exposed to immunosuppressive drugs. Human papillomavirus immunisation can be used in women with stable/inactive disease. CONCLUSIONS: Recommendations for women's health issues in SLE and/or APS were developed using an evidence-based approach followed by expert consensus.


Assuntos
Síndrome Antifosfolipídica/tratamento farmacológico , Neoplasias dos Genitais Femininos/diagnóstico , Lúpus Eritematoso Sistêmico/tratamento farmacológico , Complicações na Gravidez/tratamento farmacológico , Anticoncepcionais Orais Hormonais/uso terapêutico , Técnica Delphi , Detecção Precoce de Câncer , Terapia de Reposição de Estrogênios , Serviços de Planejamento Familiar , Feminino , Preservação da Fertilidade , Monitorização Fetal , Humanos , Menopausa , Cuidado Pré-Concepcional , Gravidez , Técnicas de Reprodução Assistida , Medição de Risco
15.
J Phys Chem A ; 121(48): 9358-9368, 2017 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-29129056

RESUMO

A computational analysis of model transition-metal terminal boride [MB(PNPR)] complexes is reported. A combination of density functional theory methods, natural bond orbital analysis, and multiconfiguration self-consistent field calculations were employed to investigate the structure and bonding of terminal boride complexes, in particular, the extent of metal dπ-boron pπ bonding. Comparison of metal-boride, -borylene, and-boryl bond lengths confirms the presence of metal-boron π bonds, albeit the modest shortening (∼3%) of the metal-boron bond suggests that the π-bonding is very weak in terminal borides. Calculated free energies of H2 addition to the boride complexes to yield the corresponding boryl complexes indicate that metal-boride π-bond strengths are 22 kcal/mol or less as compared to 44 kcal/mol for an analogous nitride complex. It is concluded that, for the boride complexes studied, covering a range of different 4d and 5d metals, that the metal-boride bond consists of a reasonably covalent σ but two very polarized metal-boron π bonds. The high polarization of the boron-to-metal π bonds indicates that the terminal boride is an acceptor or Z-type ligand.

16.
Genes Immun ; 17(6): 335-41, 2016 09.
Artigo em Inglês | MEDLINE | ID: mdl-27467286

RESUMO

Behcet's disease (BD) exhibits more severe disease course and higher mortality among male patients. However, underlying mechanisms of gender differences in clinical manifestations and disease severity are unclear. The aim of this study was to determine whether testosterone (T) has any role on BD pathogenesis. We studied peripheral blood mononuclear cells (PBMC) and neutrophils of BD patients and controls. Functional assay of neutrophils, cytokine measurements of culture supernatants and gene expressions on both cells were analyzed before and after T incubation. Neutrophils were significantly activated after incubation with T in only BD patients. Incubation with T caused significantly elevated interleukin (IL)-12 and IL-2 in BD. Gene expression of IL-10 was significantly downregulated after incubation with T in BD, especially in male patients. The same difference was observed in IL-10 levels in culture supernatant after T. Baseline TLR4 expression was significantly higher in BD patients compared to healthy donors (HC). Toll-like receptor (TLR) 4 expression on PBMC was significantly elevated in female BD patients. ERAP1 expressions of all patients and controls were decreased under the T effect but it differed significantly between BD vs HC. Baseline IL23R expression was higher in BD males compared with females but the difference disappeared after T. When BD patients were analyzed separately, baseline C-C motif chemokine receptor1 (CCR1), STAT4, TLR4 and KLRC4 expressions were lower in males. Despite immunosuppressive behavior in healthy subjects, T causes neutrophil hyperactivation and TH1 type immune alterations in BD patients. Our results suggest that T may have a role in BD pathogenesis by altering the expression level of IL-10, TLR4, ERAP1, CCR1.


Assuntos
Síndrome de Behçet/etiologia , Testosterona , Adulto , Síndrome de Behçet/genética , Síndrome de Behçet/imunologia , Citocinas/biossíntese , Feminino , Expressão Gênica , Humanos , Interleucina-10/metabolismo , Leucócitos Mononucleares/fisiologia , Masculino , Pessoa de Meia-Idade , Ativação de Neutrófilo , Neutrófilos/fisiologia , Caracteres Sexuais , Células Th1/citologia
17.
Allergy ; 71(2): 258-66, 2016 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-26449488

RESUMO

BACKGROUND: Indoleamine 2,3-dioxygenase (IDO), which degrades tryptophan (Trp) to kynurenine (Kyn), has been demonstrated to contribute to modulation of allergic responses. However, the role of IDO in food allergy has not yet been elucidated. METHODS: Serum Trp and Kyn concentrations were analyzed by high-pressure liquid chromatography. Expression of IDO gene was measured by real-time PCR. The levels of interleukin (IL)-4, IL-10, and interferon (IFN)-γ in cell culture supernatants were measured by ELISA. RESULTS: Kyn/Trp (IDO activity) was significantly lower in subjects with food allergy (n = 100) than in aged-matched healthy controls (n = 112) (P = 0.004). Kyn/Trp was decreased from healthy through completely tolerant, partially tolerant, and reactive ones [LN transformation (mean ± SEM) healthy: 3.9 ± 0.02 µM/mM; completely tolerant: 3.83 ± 0.04; partially tolerant: 3.8 ± 0.06; reactive: 3.7 ± 0.04] (P = 0.008). The frequency of genetic polymorphisms of IDO did not reveal a significant association with Trp, Kyn, and Kyn/Trp in healthy and food-allergic cases. Culture of PBMC experiments yielded that IDO mRNA expression was not different between tolerant and reactive groups. IL-4 synthesis when stimulated with casein increased significantly in subjects who are reactive and tolerant to foods (P = 0.042, P = 0.006, respectively). Increase in IL-10 synthesis was observed only in children tolerant to milk, but not in reactive ones. IFN-γ synthesis, when stimulated with IL-2 and ß-lactoglobulin in cell culture, was significantly higher in subjects tolerant to milk than in the reactive ones (P = 0.005 and P = 0.029, respectively). CONCLUSION: Our results imply the probability of involvement of IDO in development of tolerance process, and we presume that high IDO activity is associated with nonresponsiveness to food allergens despite allergen sensitization.


Assuntos
Hipersensibilidade Alimentar/sangue , Hipersensibilidade Alimentar/imunologia , Indolamina-Pirrol 2,3,-Dioxigenase/sangue , Alelos , Biomarcadores , Estudos de Casos e Controles , Criança , Pré-Escolar , Citocinas , Ensaio de Imunoadsorção Enzimática , Feminino , Hipersensibilidade Alimentar/diagnóstico , Hipersensibilidade Alimentar/genética , Expressão Gênica , Frequência do Gene , Genótipo , Humanos , Imunoglobulina E/sangue , Imunoglobulina E/imunologia , Indolamina-Pirrol 2,3,-Dioxigenase/genética , Lactente , Cinurenina/sangue , Masculino , Fenótipo , Polimorfismo de Nucleotídeo Único , Prognóstico , Triptofano/sangue
19.
Clin Exp Ophthalmol ; 43(2): 139-44, 2015 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-24995937

RESUMO

BACKGROUND: To assess the choroidal thickness (CT) in patients with obstructive sleep apnoea syndrome (OSAS) and healthy controls. DESIGN: Prospective, cross-sectional study PARTICIPANTS: Ninety-two eyes of 92 patients with OSAS and 32 eyes of 32 aged and body mass index-matched healthy subjects were enrolled. METHODS: OSAS patients were further divided into mild, moderate and severe OSAS groups according to their apnoea hypopnea index (AHI) values. The macular CT and peripapillary retinal nerve fibre layer (RNFL) thickness measurements of the subjects were obtained using spectral domain optical coherence tomography (RTVue-100, Optovue). The CT and RNFL thickness measurements of the groups were compared, and correlations among the AHI values and these measurements were calculated. MAIN OUTCOME MEASURES: Choroidal thickness. RESULTS: There were no significant differences in subfoveal and temporal CT measurements of the groups. A pairwise comparison between the groups revealed that severe OSAS group has significantly thinner CT than mild OSAS group at 3.0 mm nasal to the fovea. Also, compared with severe OSAS group, the CT measurements at 1.5 mm and 3.0 mm nasal to the fovea were significantly thicker in control eyes (both, P < 0.05). There were weak negative correlations between the nasal CT measurements and AHI in the OSAS group (nasal 1.5 mm, P = 0.002, r = -0.358; nasal 3.0 mm, P = 0.004, r = -0.336). Compared with controls, severe OSAS group had significantly thinner nasal and superior RNFL thickness measurement. CONCLUSIONS: Sleep apnoea patients had choroidal structural alterations that may have significance on the pathophysiology of the ophthalmic disorders associated with OSAS.


Assuntos
Corioide/patologia , Apneia Obstrutiva do Sono/complicações , Adulto , Comprimento Axial do Olho/anatomia & histologia , Índice de Massa Corporal , Estudos Transversais , Feminino , Voluntários Saudáveis , Humanos , Pressão Intraocular , Masculino , Pessoa de Meia-Idade , Fibras Nervosas/patologia , Tamanho do Órgão , Estudos Prospectivos , Células Ganglionares da Retina/patologia , Apneia Obstrutiva do Sono/diagnóstico , Tomografia de Coerência Óptica
20.
Int Endod J ; 48(10): 986-93, 2015 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-25286824

RESUMO

AIM: To evaluate the cytotoxicity and mineralization effects of iRoot BP in human dental pulp cells (hDPCs) and to compare them with those of white mineral trioxide aggregate (WMTA). METHODOLOGY: hDPCs were exposed to prepared dilutions (1 : 1-1 : 10) of the test materials. Cell viability was evaluated using the XTT assay after incubation periods of 24, 48 or 72 h. The expression of mineralization-related genes (bone morphogenic protein, osteonectin, bone sialoprotein, osteopontin, dentine sialophosphoprotein and collagen type 1) and heme oxygenase 1 was measured by quantitative real-time polymerase chain reaction (qRT-PCR) at 24 and 72 h. Statistical differences between test materials were analysed with the Mann-Whitney test. RESULTS: The 1 : 1 and 1 : 2 dilutions of iRoot BP were associated with higher cell viability after 24 h (P < 0.05). Only the 1 : 1 dilution of iRoot BP had higher cell viability after 48 h (P < 0.05), and there was no difference between iRoot BP and WMTA after 72 h (P > 0.05). Although somewhat variable, according to the gene expression results, iRoot BP had a mineralization potential similar to that of WMTA. WMTA revealed a higher heme oxygenase 1 (HO-1) mRNA level than iRoot BP (P < 0.001). CONCLUSIONS: iRoot BP and WMTA were biocompatible and facilitated odontoblastic differentiation of hDPCs.


Assuntos
Compostos de Alumínio/toxicidade , Compostos de Cálcio/toxicidade , Sobrevivência Celular/efeitos dos fármacos , Polpa Dentária/citologia , Expressão Gênica , Osteogênese/efeitos dos fármacos , Osteogênese/genética , Óxidos/toxicidade , Silicatos/toxicidade , Proliferação de Células/efeitos dos fármacos , Células Cultivadas , Combinação de Medicamentos , Humanos , Técnicas In Vitro , Dente Molar , Reação em Cadeia da Polimerase em Tempo Real
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