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2.
Chemistry ; 30(33): e202400915, 2024 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-38616170

RESUMO

A new concept for the regioselective synthesis of Hamilton-receptor and cyanurate-functionalized oligo adducts of the fullerene C60 was developed. Based on an in-situ deprotection and click-post-functionalization approach with novel azido precursors, the corresponding fullerene hexakis-adducts with octahedral addition patterns and up to twelve Hamilton-receptor/cyanurate moieties surrounding the fullerene sphere were synthesized. The versatility of this approach was further demonstrated by the synthesis of Hamilton-receptor/cyanurate functionalized fullerene mono-adducts, which are not accessible by direct cyclopropanation. Several fullerene target compounds were purified by simple washing procedures of the solid crude reaction mixture without the need for chromatography. The resulting fullerene mono- and hexakis-adducts were fully characterized and their supramolecular properties were investigated by NMR-spectroscopy and isothermal titration calorimetry (ITC).

3.
Artigo em Inglês | MEDLINE | ID: mdl-38387784

RESUMO

INTRODUCTION: Freehand SPECT can be a useful imaging technique for preoperative planning of sentinel lymph node biopsy (SLNB) as it allows localization of the sentinel node by 3D and real-time tomographic imaging and determines its depth after a few minutes of scanning. The aim of the study was to evaluate the correlation between the number of detected SNs between freehand SPECT images and lymphoscintigraphy (LS). MATERIALS AND METHODS: 100 patients with a diagnosis of invasive breast cancer and no clinical evidence of lymph node involvement prospectively underwent SLNB. The preoperative study included freehand SPECT imaging at 15min after injection and LS imaging at 25 and 60-90min after injection (early and late). The observed agreement was analyzed and a concordance study was performed between the number of SNs detected with freehand SPECT and LS. RESULTS: The observed agreement in the detection of SNs between freehand SPECT and early LS was 72%; between freehand SPECT and late LS was 85%; and between early and late LS was 87%. In the concordance study, there was moderate concordance between freehand SPECT and early LS (kappa coefficient: 0.42); moderate-high concordance between freehand SPECT and late LS (kappa coefficient: 0.60); and moderate-high concordance between early and late LS (kappa coefficient: 0.70), with no significant differences between them (p-value=0.16). CONCLUSION: Freehand SPECT showed a moderate-high concordance with conventional imaging studies and could be a valid alternative for the presurgical study of SLNB in breast cancer.


Assuntos
Neoplasias da Mama , Linfonodo Sentinela , Humanos , Feminino , Linfonodo Sentinela/diagnóstico por imagem , Linfonodo Sentinela/patologia , Neoplasias da Mama/diagnóstico por imagem , Neoplasias da Mama/cirurgia , Neoplasias da Mama/patologia , Biópsia de Linfonodo Sentinela/métodos , Tomografia Computadorizada de Emissão de Fóton Único/métodos , Linfonodos/patologia
5.
Chemistry ; 29(70): e202303814, 2023 Dec 14.
Artigo em Inglês | MEDLINE | ID: mdl-38019120

RESUMO

Invited for the cover of this issue are the groups of Alexander S. Oshchepkov, Konstantin Y. Amsharov, and M. Eugenia Pérez-Ojeda at the Max Planck Institute for the Science of Light, Martin-Luther-University Halle-Wittenberg and Friedrich-Alexander-Universität Erlangen-Nürnberg, respectively. The image depicts a buckybowl catcher carefully framing the C70 fullerene which is associated with miraculous, marvellous Fabergé artworks. Read the full text of the article at 10.1002/chem.202302778.

6.
Chemistry ; 29(70): e202302778, 2023 Dec 14.
Artigo em Inglês | MEDLINE | ID: mdl-37801357

RESUMO

A novel buckybowl catcher with an extended π-surface has been synthesized via cross-coupling of two bowl shaped bromoindacenopicene moieties with a tolyl linker. The obtained catcher has been unambiguously characterized by 2D-NMR and mass spectrometry. DFT calculations indicate that the curved shape of the receptor moieties is favourable for binding fullerenes. Effective binding was confirmed for interactions with C60 and C70 utilizing NMR spectroscopy and isothermal titration calorimetry (ITC). The resulting binding values show a higher affinity of the catcher towards C70 over C60 . The designed catcher demonstrated the fundamental possibility of creating sensors for spherical aromaticity.

7.
J Am Chem Soc ; 145(40): 22252-22264, 2023 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-37773090

RESUMO

The amount of unfolded proteins is increased in cancer cells, leading to endoplasmic reticulum (ER) stress. Therefore, cancer cells are sensitive to drugs capable of further enhancing ER stress. Examples of such drugs include the clinically approved proteosome inhibitors bortezomib and carfilzomib. Unfortunately, the known ER stress inducers exhibit dose-limiting side effects that justify the search for better, more cancer-specific drugs of this type. Herein, we report on FeC 2, which binds to unfolded proteins prevents their further processing, thereby leading to ER stress and ROS increase in cancer cells, but not in normal cells. FeC 2 exhibits low micromolar toxicity toward human acute promyelocytic leukemia HL-60, Burkitt's lymphoma BL-2, T-cell leukemia Jurkat, ovarian carcinoma A2780, lung cancer SK-MES-1, and murine lung cancer LLC1 cells. Due to the cancer-specific mode of action, 2 is not toxic in vivo up to the dose of 147 mg/kg, does not affect normal blood and bone marrow cells at the therapeutically active dose, but strongly suppresses both primary tumor growth (confirmed in Nemeth-Kellner lymphoma and LLC1 lung cancer models of murine tumor) and spreading of metastases (LLC1).

8.
J Am Chem Soc ; 145(30): 16517-16525, 2023 Aug 02.
Artigo em Inglês | MEDLINE | ID: mdl-37467341

RESUMO

High-throughput synthesis of solution-processable structurally variable small-molecule semiconductors is both an opportunity and a challenge. A large number of diverse molecules provide a possibility for quick material discovery and machine learning based on experimental data. However, the diversity of the molecular structure leads to the complexity of molecular properties, such as solubility, polarity, and crystallinity, which poses great challenges to solution processing and purification. Here, we first report an integrated system for the high-throughput synthesis, purification, and characterization of molecules with a large variety. Based on the principle "Like dissolves like," we combine theoretical calculations and a robotic platform to accelerate the purification of those molecules. With this platform, a material library containing 125 molecules and their optical-electronic properties was built within a timeframe of weeks. More importantly, the high repeatability of recrystallization we design is a reliable approach to further upgrading and industrial production.

9.
Chemistry ; 29(44): e202301061, 2023 Aug 04.
Artigo em Inglês | MEDLINE | ID: mdl-37199454

RESUMO

The synthesis and characterization of four dumbbell-shaped fullerene molecules connected by isosorbide and isomannide moieties is presented. Additionally, their electrochemical behavior and their ability to form complexes with [10]cycloparaphenylene ([10]CPP) were investigated. The cyclic voltammetry (CV) results of the fullerene dumbbells demonstrate a high electron affinity, indicating their strong interaction with electron-donating counterparts such as carbon nanorings, which possess complementary charge and shape properties. To study the thermodynamic and kinetic parameters of complexation, isothermal titration calorimetry (ITC) was employed. NMR titration experiments provided further insights into the binding stoichiometries. Two distinct approaches were utilized to create bridged structures: one based on cyclopropane and the other based on furan. Regardless of the type of linker used, all derivatives formed conventional 2 : 1 complexes denoted as [10]CPP2 ⊃C60derivative . However, the methano-dumbbell molecules exhibited distinct binding behavior, resulting in the formation of mono- and bis-pseudorotaxanes, as well as oligomers (polymers). The formation of linear polymers holds significant potential for applications in solar energy conversion processes.

10.
Nanoscale ; 15(12): 5665-5670, 2023 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-36896752

RESUMO

In this work, we compare for the first time the stability of [n]cycloparaphenylene ([n]CPP)-based host-guest complexes with Li+@C60 and C60 in the gas and the solution phase. Our gas-phase experiments reveal a significant increase in stability for the complexes featuring [9-12]CPP with Li+@C60. This increased interaction strength is also observed in solution. Isothermal titration calorimetry shows for the formation of [10]CPP⊃Li+@C60 a two orders of magnitude larger association constant than that for the C60 analog. Additionally, an increased binding entropy is observed. This study contributes to a better understanding of host-guest complexes between [n]CPPs and endohedral metallofullerenes at a molecular level, which is the prerequisite for future applications.

12.
Chemistry ; 29(16): e202203734, 2023 Mar 16.
Artigo em Inglês | MEDLINE | ID: mdl-36507855

RESUMO

We investigate the gas-phase chemistry of noncovalent complexes of [10]cycloparaphenylene ([10]CPP) with C60 and C70 by means of atmospheric pressure photoionization and electrospray ionization mass spectrometry. The literature-known [1 : 1] complexes, namely [10]CPP⊃C60 and [10]CPP⊃C70 , are observed as radical cations and anions. Their stability and charge distribution are studied using energy-resolved collision-induced dissociation (ER-CID). These measurements reveal that complexes with a C70 core exhibit a greater stability and, on the other hand, that the radical cations are more stable than the respective radical anions. Regarding the charge distribution, in anionic complexes charges are exclusively located on C60 or C70 , while the charges reside on [10]CPP in the case of cationic complexes. [2 : 1] complexes of the ([10]CPP2 ⊃C60/70 )+ ⋅/- ⋅ type are observed for the first time as isolated solitary gas-phase species. Here, C60 -based [2 : 1] complexes are less stable than the respective C70 analogues. By virtue of the high stability of cationic [1 : 1] complexes, [2 : 1] complexes show a strongly reduced stability of the radical cations. DFT analyses of the minimum geometries as well as molecular dynamics calculations support the experimental data. Furthermore, our novel gas-phase [2 : 1] complexes are also found in 1,2-dichlorobenzene. Insights into the thermodynamic parameters of the binding process as well as the species distribution are derived from isothermal titration calorimetry (ITC) measurements.

13.
BMC Pregnancy Childbirth ; 22(1): 836, 2022 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-36376827

RESUMO

BACKGROUND: Every woman expresses pain differently during birth since it depends on a multitude of predictive factors. The medical care received, companionship during birth, cultural background and language barriers of the women in labour can influence on the expression of pain. This study aims to evaluate the expression of pain during birth and its associated factors in women treated in a Spanish border town. METHODS: The study included 246 women in labour. The expression of pain during labour was evaluated using the validated ESVADOPA scale. A descriptive analysis and association study were performed between cultural identity and dimensions of the scale. Multiple linear regression models were performed to assess the association between cultural identity, origin, language barrier, and companionship during labour. RESULTS: The women included in the study comprised 68.7% Berbers, 71.5% Muslims and 82.1% were accompanied during labour. An association between cultural identity and greater body expression of pain (p = 0.020; Cramer's V = 0.163) in addition to its verbal expression was found during the latent phase of labour, (p = 0.028; Cramer's V = 0.159). During the active phase of labour, cultural identity was associated with pain expression through greater body response, verbal expression, expression of the facial muscles, anxiety, inability to relax and vegetative symptoms. The different factors studied that had a predictive value were companionship (p = 0.027) during the latent phase of labour and Berber origin (p = 0.000), language barrier (p = 0.014) and companionship (p = 0.005) during the active phase of labour. The models designed predict pain expression in the latent phase by companionship and type of companionship (ß = 1.483; 95%CI = 0.459-2.506, ß = 0.238; 95%CI = 0.029-0. 448, respectively), and in the active phase by background, language barrier and companionship (ß = 0.728; 95%CI = 0.258-1.198, ß = 0.738; 95%CI = 0.150-1.326, ß = 1.888; 95%CI = 0.984-2.791, respectively). CONCLUSION: Culture, origin, language barrier and companionship during labour influences the manner in which women in labour express their pain. An understanding of this may help midwives correctly interpret the signs of pain expression and be able to offer the appropriate assistance depending on a woman's particular characteristics. There is a clear need for new models of maternity care that will take the cultural and language characteristics of women in labour into consideration.


Assuntos
Dor do Parto , Trabalho de Parto , Serviços de Saúde Materna , Tocologia , Feminino , Gravidez , Humanos , Tocologia/métodos , Parto
14.
Rev Gastroenterol Mex (Engl Ed) ; 87(3): 342-361, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35879225

RESUMO

Ulcerative colitis (US) is a chronic disease of unknown etiology. It is incurable and its clinical course is intermittent, characterized by periods of remission and relapse. The prevalence and incidence of the disease has been increasing worldwide. The update presented herein includes the participation of healthcare professionals, decision-makers, and a representative of the patients, all of whom declared their conflicts of interest. Answerable clinical questions were formulated, and the outcomes were graded. The information search was conducted on the Medline/PubMed, Embase, Epistemonikos, and LILACS databases, and covered grey literature sources, as well. The search was updated on November 30, 2020, with no restrictions regarding date or language. The Grading of Recommendations Assessment, Development and Evaluation (GRADE) classification system was implemented to establish the strength of the recommendation and quality of evidence. A formal consensus was developed, based on the RAND/UCLA methodology and the document was peer reviewed. The short version of the Clinical Practice Guidelines for the Treatment of Ulcerative Colitis in the Adult Population is presented herein, together with the supporting evidence and respective recommendations. In mild-to-moderate UC, budesonide MMX is an option when treatment with 5-ASA fails, and before using systemic steroids. In moderate-to-severe UC, infliximab, adalimumab, vedolizumab, ustekinumab, and tofacitinib can be used as first-line therapy. If there is anti-TNF therapy failure, ustekinumab and tofacitinib provide the best results. In patients with antibiotic-refractory pouchitis, anti-TNFs are the treatment of choice.


Assuntos
Colite Ulcerativa , Adalimumab/uso terapêutico , Adulto , Colite Ulcerativa/tratamento farmacológico , Humanos , Infliximab/uso terapêutico , Inibidores do Fator de Necrose Tumoral , Ustekinumab/uso terapêutico
15.
An Sist Sanit Navar ; 45(2)2022 Jul 01.
Artigo em Espanhol | MEDLINE | ID: mdl-35786708

RESUMO

BACKGROUND: The clinical spectrum of COVID-19 varies from no or mild symptoms to pneumonia with fatal complications. The aim of the study was to find predictors of mortality and admission in the intensive care unit (ICU) in patients hospitalized for COVID-19. METHODS: Retrospective study of a cohort of patients admitted for COVID-19 between March 2020 and February 2021. Demographic, clinical, radiological and laboratory variables were described at admission. Independent predictors of mortality and ICU admission were identified by means of backward stepwise logistic regression and described in terms of odds ratio (OR) and 95% confidence interval (95%CI). RESULTS: A total of 883 patients were included, 51.8% men with a mean age of 68; 1.8% readmissions. 17.6% of patients died (n=154). The independent predictors of mortality were age (OR=1.071; 95%CI: 1.046-1.095), percentage of oxygen saturation (SatO2) (OR=0.938; 95%CI: 0.903-0.974), diastolic blood pressure (DBP, OR= 0.972; 95%CI: 0.955-0.989), creatinine (OR=1.516; 95%CI: 1.088-2.113), INR (OR=1.199; 95%CI: 1.012-1.419) and sodium (OR=1.082; 95%CI: 1.037-1.128). Eight percent of patients were admitted to ICU; the independent predictors were: male sex (OR=2.079; 95%CI: 1.099-3.935), age (OR=0.960; 95%CI: 0.942-0.979), SatO2 (OR=0.925; 95%CI: 0.889-0.962), creatinine (OR=1.551; 95%CI: 1.118-2.152) and C-reactive protein (CRP, OR=1.003; 95%CI: 1.000-1.007). CONCLUSION: The identification of independent predictors of mortality (age, SatO2, DBP, creatinine, INR, sodium) and ICU admission (sex, age, SatO2, creatinine, and CRP) allowed for the stratification of patients to adapt clinical care protocols to these findings, thereby improving medical decisions.


Assuntos
COVID-19 , Idoso , Proteína C-Reativa , Creatinina , Feminino , Humanos , Masculino , Prognóstico , Estudos Retrospectivos , Sódio
16.
An. sist. sanit. Navar ; 45(2): [e1000], Jun 29, 2022. tab
Artigo em Espanhol | IBECS | ID: ibc-208794

RESUMO

Fundamento: El espectro clínico de la COVID-19 varía entre sintomatología leve o ausente hasta neumonías con complicaciones mortales. El objetivo del estudio fue determinar los factores predictivos de mortalidad e ingreso en cuidados intensivos (UCI) en pacientes hospitalizados por COVID-19. Metodología: Estudio retrospectivo de una cohorte de pacientes ingresados por COVID-19 entre marzo de 2020 y febrero de 2021. Se describieron las variables demográficas, clínicas, radiológicas y analíticas al ingreso. Los predictores independientes de mortalidad e ingreso en UCI se identificaron mediante regresión logística por pasos hacia atrás y se describieron como odds ratio (OR) e intervalo de confianza al 95% (IC95%). Resultados: Se incluyeron 883 pacientes, 51,8% varones y edad media 68 años; el 1,8% reingresó. Fallecieron 154 pacientes (17,6%); los predictores independientes de mortalidad fueron: edad (OR=1,071; IC95%: 1,046-1,095), porcentaje de saturación de oxígeno (SatO2) (OR=0,938; IC95%: 0,903-0,974), tensión arterial diastólica (PAD, OR=0,972; IC95%: 0,955-0,989), creatinina (OR=1,516; IC95%: 1,088-2,113), INR (OR=1,199; IC95%: 1,012-1,419) y sodio (OR=1,082; IC95%: 1,037-1,128). El 8% de los pacientes ingresaron en UCI; las variables predictoras independientes fueron: sexo masculino (OR=2,079; IC95%: 1,099-3,935), edad (OR=0,960; IC95%: 0,942-0,979), SatO2 (OR=0,925; IC95%: 0,889-0,962), creatinina (OR=1,551; IC95%: 1,118-2,152) y proteína C reactiva (PCR, OR=1,003; IC95%: 1,000-1,007). Conclusiones: La identificación de predictores independientes de mortalidad (edad, SatO2, PAD, creatinina, INR, sodio) y de ingreso en UCI (sexo, edad, SatO2, creatinina y PCR) permite estratificar a los pacientes y adaptar los protocolos de atención clínica a estos hallazgos, mejorando las decisiones médicas.(AU)


Background: The clinical spectrum of COVID-19 varies from no or mild symptoms to pneumonia with fatal complications. The aim of the study was to find predictors of mortality and admis-sion in the intensive care unit (ICU) in patients hospitalized for COVID-19. Methods: Retrospective study of a cohort of patients admitted for COVID-19 between March 2020 and February 2021. Demographic, clinical, radiological and laboratory variables were described at admission. Independent predictors of mortality and ICU admission were identified by means of backward stepwise logistic regression and described in terms of odds ratio (OR) and 95% confidence interval (95%CI). Results: A total of 883 patients were included, 51.8% men with a mean age of 68; 1.8% readmissions. 17.6% of patients died (n=154). The independent predictors of mortality were age (OR=1.071; 95%CI: 1.046-1.095), percentage of oxygen saturation (SatO2) (OR=0.938; 95%CI: 0.903-0.974), diastolic blood pressure (DBP, OR= 0.972; 95%CI: 0.955-0.989), creatinine (OR=1.516; 95%CI: 1.088-2.113), INR (OR=1.199; 95%CI: 1.012-1.419) and sodium (OR=1.082; 95%CI: 1.037-1.128). Eight percent of patients were admitted to ICU; the independent predictors were: male sex (OR=2.079; 95%CI: 1.099-3.935), age (OR=0.960; 95%CI: 0.942-0.979), SatO2 (OR=0.925; 95%CI: 0.889-0.962), creatinine (OR=1.551; 95%CI: 1.118-2.152) and C-reactiveprotein (CRP, OR=1.003; 95%CI: 1.000-1.007). Conclusion: The identification of independent predictors of mortality (age, SatO2, DBP, creatinine, INR, sodium) and ICU admission (sex, age, SatO2, creatinine, and CRP) allowed for the stratification of patients to adapt clinical care protocols to these findings, thereby improving medical decisions.(AU)


Assuntos
Humanos , Masculino , Feminino , Prognóstico , Infecções por Coronavirus/epidemiologia , Coronavírus Relacionado à Síndrome Respiratória Aguda Grave , Betacoronavirus , Pacientes Internados , Mortalidade , Pneumonia , Unidades de Terapia Intensiva , Sistemas de Saúde , Espanha , Estudos Retrospectivos , Estudos de Coortes
17.
J Healthc Qual Res ; 37(5): 303-312, 2022.
Artigo em Espanhol | MEDLINE | ID: mdl-35165076

RESUMO

INTRODUCTION AND OBJECTIVE: Hip fracture in the elderly leads to long hospital stays, readmissions and mortality. OBJECTIVE: To identify risk factors associated with mortality and readmissions in elderly with hip fracture. PATIENTS AND METHODS: Prospective observational study in people over 65years with hip fracture between October-2017 and November-2018, followed for 12months (128 patients). STATISTICAL ANALYSIS: SPSS vs27.0. RESULTS: 6 (4.7%) patients were readmitted at 1 month; at year 24 (19.4%); 55 (44.4%) consulted for emergencies; 4 (3.1%) died during admission, and 26 (20.3%) in 12months; hospital stay 6.5 (SD: 4.80) days. Those with a previous Barthel less than 85 (6 [8.5%] vs 0 [0%]; P=.037) and less EuroQol5D (6 [10.0] vs 0 [0%]; P=.011) were readmitted more at one month. Those taking anticoagulants (OR: 3.33 (1.13-9.81); P=.003) and those with high surgical risk (18 [23.4%] vs 1 [5.6%]) were readmitted more after one year; P=.038). There was higher intra-episode mortality with renal failure (OR: 34.2 [3.25-359.93]; P=.003) and decompensated heart failure (OR: 23.8 [2.76-205.25]; P=.015). Higher mortality at one year in those older than 85years (OR: 4.3 [1.48-12.49]; P=.007); in those taking benzodiazepines (OR: 2.86 [1.06-7.73]; P=.038); if Barthel was less than 85 (OR: 2.96 [1.1-7.99]; P=.027) and if EuroQol5D was low (0.249 vs 0.547; P=.025). Those operated after 72h (24 [57.1%] vs. 29 [38.2%]; P=.047) consulted more for the emergency department. CONCLUSIONS: Renal failure and cardiac decompensation increased intra-episode mortality. Older age, benzodiazepines, and previous low functionality and low EuroQol5D increased mortality at one year. They were readmitted more if higher surgical risk, previously anticoagulated and worse quality of life and functionality.


Assuntos
Fraturas do Quadril , Fraturas por Osteoporose , Insuficiência Renal , Idoso , Anticoagulantes , Benzodiazepinas , Fraturas do Quadril/cirurgia , Humanos , Fraturas por Osteoporose/cirurgia , Readmissão do Paciente , Qualidade de Vida , Fatores de Risco
18.
Acta Ortop Mex ; 35(2): 211-214, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34731926

RESUMO

Epithelioma cuniculatum is characterized as a slow growing lesion on the sole of the foot. A diagnosis is usually delayed by a low clinical suspicion and misdirection due to its similarity to an infection. This tumor rarely metastasize but a local invasion of adjacent soft tissues is common, requiring ample surgical resection or even amputation in advanced cases. We report a case a 76-year-old patient with a 5-year-old lesion on the sole of the foot, which was originally treated as a wart without improvement while the lesion slowly evolved. The patient was referred to our center with a diagnosis of chronic osteomyelitis. An excisional biopsy revealed an invasive keratinizing squamous carcinoma. In this advanced phase of the disease the only possible treatment was a Syme amputation.


El epitelioma cuniculatum se caracteriza por una lesión de crecimiento lento en la planta del pie cuyo diagnóstico suele retrasarse por la baja sospecha clínica y por su similitud con una infección. Este tumor raramente metastatiza, pero es común que produzca una invasión local a los tejidos blandos adyacentes, requiriendo una amplia resección quirúrgica o incluso una amputación en casos avanzados. Presentamos un caso de un paciente de 76 años con una lesión de 5 años de edad en la planta del pie, que originalmente fue tratada como una verruga plantar común sin mejoría, mientras que la lesión evolucionó lentamente. El paciente fue remitido a nuestro centro con un diagnóstico de osteomielitis crónica. Una biopsia excisional reveló un carcinoma escamoso queratinizante invasivo. En esta fase avanzada de la enfermedad el único tratamiento posible fue una amputación de Syme.


Assuntos
Neoplasias Ósseas , Carcinoma Verrucoso , Doenças do Pé , Idoso , Amputação Cirúrgica , Pré-Escolar , , Doenças do Pé/diagnóstico , Doenças do Pé/cirurgia , Humanos
19.
J Am Chem Soc ; 143(45): 18997-19007, 2021 11 17.
Artigo em Inglês | MEDLINE | ID: mdl-34699723

RESUMO

Herein we report the synthesis of covalently functionalized carbon nano-onions (CNOs) via a reductive approach using unprecedented alkali-metal CNO intercalation compounds. For the first time, an in situ Raman study of the controlled intercalation process with potassium has been carried out revealing a Fano resonance in highly doped CNOs. The intercalation was further confirmed by electron energy loss spectroscopy and X-ray diffraction. Moreover, the experimental results have been rationalized with DFT calculations. Covalently functionalized CNO derivatives were synthesized by using phenyl iodide and n-hexyl iodide as electrophiles in model nucleophilic substitution reactions. The functionalized CNOs were exhaustively characterized by statistical Raman spectroscopy, thermogravimetric analysis coupled with gas chromatography and mass spectrometry, dynamic light scattering, UV-vis, and ATR-FTIR spectroscopies. This work provides important insights into the understanding of the basic principles of reductive CNOs functionalization and will pave the way for the use of CNOs in a wide range of potential applications, such as energy storage, photovoltaics, or molecular electronics.

20.
Am J Drug Alcohol Abuse ; 47(6): 680-693, 2021 Nov 02.
Artigo em Inglês | MEDLINE | ID: mdl-34582310

RESUMO

BACKGROUND: Binge drinking (BD) during adolescence is related to cardiovascular alterations. Selenium (Se) is an essential trace element with antioxidant, anti-inflammatory and antiapoptotic properties, essential for correct heart function. OBJECTIVES: To study the protective cardiovascular effects of selenium in adolescent rats exposed to a BD-like procedure. METHODS: 32 adolescent male rats exposed to an intraperitoneally BD-like model or not, and supplemented with 0.4ppm of selenite or not, were divided into 4 groups: control, alcohol, control-selenium and alcohol-selenium. Blood pressure and heart rate (HR) were determined after experimentation. Se deposits, oxidative balance and the expression of glutathione peroxidases (GPxs), NF-kB and caspase-3 were measured in the heart. Also, DNA instability in rat lymphocytes and serum vascular markers were determined. Statistical analysis was performed with the ANOVA model. RESULTS: The BD-like model depleted Se heart deposits (p < .01), decreased GPx activity (p < .01) and GPx1 (p < .001) and GPx4 (p < .05) expression, increased NF-kB (p < .01), caspase-3 (p < .001) expression, and generated oxidation in myocytes. Outside the heart, the BD-like model caused double-strand breaks in lymphocyte DNA and increased all the vascular markers measured. These cardiovascular alterations were related to higher systolic (p < .001) and diastolic (p < .05) blood pressure and HR (p < .05). In the heart, Se supplementation in BD-exposed rats significantly increased Se deposits (p < .001) and improved oxidative balance and vascular damage, including increased GPxs and decreased NF-kB and caspase-3 activation, consequently decreasing systolic (p < .05) blood pressure and HR (p < .01). CONCLUSIONS: Se supplementation presents cardioprotective effects since it reversed HR and systolic blood pressure observed in BD-exposed adolescent rats.


Assuntos
Consumo Excessivo de Bebidas Alcoólicas , Selênio , Animais , Antioxidantes/metabolismo , Antioxidantes/farmacologia , Antioxidantes/uso terapêutico , Consumo Excessivo de Bebidas Alcoólicas/tratamento farmacológico , Pressão Sanguínea , Frequência Cardíaca , Humanos , Fígado , Masculino , Estresse Oxidativo , Ratos , Ratos Wistar , Selênio/metabolismo , Selênio/uso terapêutico
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