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1.
Environ Sci Pollut Res Int ; 31(8): 11983-11994, 2024 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-38225500

RESUMEN

The western-European hedgehog (Erinaceus europaeus) is an insectivore with a wide distribution in Portugal and a potential tool for biomonitoring relevant One Health hazards, including heavy metal(loid)s' pollution. The aim of this study was to positively contribute to the current knowledge about the metal(loid) pollution in Portugal. Forty-six hedgehogs (from rescue centres; with known provenance) were necropsied. Sex, age category and weight were determined. Spines, liver and kidney were collected, and metalloid concentrations were determined by inductively coupled plasma mass spectrophotometry (ICP-MS). In general, results did not present alarming metal(loid) concentrations, with the exception of cadmium (Cd) (in the kidneys) and copper (Cu). Hedgehogs from Viana do Castelo and Viseu showed elevated concentrations of arsenic (As) and Castelo Branco presented concerning values of cadmium (Cd). Adult and heavier hedgehogs tended to present higher levels of metal(loid)s. Sex does not seem to significantly affect the metal(loid)s' concentrations. Further analysis would be needed to prioritize areas with detail and allow the application of the necessary mitigation strategies.


Asunto(s)
Metaloides , Metales Pesados , Animales , Cadmio/análisis , Portugal , Erizos , Monitoreo del Ambiente/métodos , Metales Pesados/análisis , Metaloides/análisis , China , Medición de Riesgo
2.
Res Sports Med ; : 1-15, 2023 May 30.
Artículo en Inglés | MEDLINE | ID: mdl-37254515

RESUMEN

This study aimed to evaluate the immediate effect of Dynamic TapeTM (DT) on hip muscle activation and torque and on lower limb kinematics. Forty-five healthy, recreationally active women were randomly assigned to three groups: 1) submitted to the application of DT in the active form in the gluteus medius (GMed) muscle (BG; n = 15), 2) submitted to the application of DT in the placebo form in the GMed muscle (PG; n = 15), and 3) not submitted to any intervention (CG; n = 15). Participants were evaluated for GMed and gluteus maximus (GMax) muscle activation in a maximal voluntary isometric contraction, simultaneously with the assessment of the hip abductor and extensor torques, as well as during two functional tasks - single leg squat (SLS) and jump landing + maximum vertical jump (VJ) - simultaneously with a 2-D kinematic assessment of the lower limb. After DT application in BG, there was a significant decrease in the hip abductor time to peak torque (P = 0.004), hip extensor torque (P = 0.02), excursion to hip adduction (P = 0.007), and to knee flexion (P = 0.02) during the SLS, as well as in GMed activation during VJ (P < 0.05). DT was able to reduce GMed activation and modify lower limb torque and kinematics.

3.
J Voice ; 37(1): 9-16, 2023 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-33046277

RESUMEN

Cepstral measures are sensitive to gender, age and phonatory tasks. With a cepstral measure designated as the CPP, it was possible to confirm the vulnerability of the Fado singers' voice. These were established at the vocal pathological threshold, which suggests a need for a direct clinical approach for these voice users. OBJECTIVES/HYPOTHESIS: This study aimed to characterize cepstral peak prominence (CPP) and cepstral peak prominence smoothed (CPPS) in the Fado singing voice and to determine if there were significant differences in CPP and CPPS measures between spoken and sung tasks, as well as due to singers' gender and age. METHODS: Forty seven males and 57 females Fado singers, ranging from 18 to 70 years participated in this study. Spoken voice tasks were sustained [a] and reading aloud the phonetically balanced text "O Sol". Sung tasks were sustained [a] of the word [ɐfinaÉ«] and the Fado chorus song "Nem às paredes confesso". Acoustic measures included CPP and CPPS. CPP was measured using Analyses of Dysphonia in Speech and Voice software, of Multi-Speech program, Model 3700, by KayPENTAX. CPPS was measured using Praat software (4.2.1/2003). Statistical analysis was performed with an IBM SPSS Statistics version 22 program. CPP and CPPS mean differences of spoken and sung tasks were analyzed using paired samples t-test, with α at .05. RESULTS: CPP and CPPS values of singers' voice changed according to the gender, age and phonatory tasks. There were significant differences between CPP and CPPS measures (P < 0.05). Generally, young male singers, in their sung task, presented the highest CPP and CPPS values. The highest CPP mean was obtained by older males in sustained spoken [a] and the lowest was obtained by younger males in their reading aloud task. For CPPS, the highest mean value was obtained by younger males during sung [a] and the lowest was by younger males in the reading aloud task. CONCLUSION: Males presented higher cepstral measures than females. Young singers presented higher cepstral measures than older. Sung tasks had higher cepstral measures than spoken tasks. CPPS means are overall higher than CPP means. This study reinforces the need for a clinical prevention approach directed at potential vocal disorders in Fado singers.


Asunto(s)
Disfonía , Voz , Femenino , Masculino , Humanos , Acústica del Lenguaje , Calidad de la Voz , Fonación
4.
Vector Borne Zoonotic Dis ; 19(9): 708-710, 2019 09.
Artículo en Inglés | MEDLINE | ID: mdl-30990772

RESUMEN

Introduction: In 2011, Schmallenberg virus (SBV) was first detected in dairy cattle herds in The Netherlands and Germany having since then spread across Europe. Today studies are starting to show a decrease in new SBV infections, a circumstance that raises alerts for possible re-emergence if ideal conditions for vector development occur. To assess the potential decrease in SBV circulation, we performed a 2-year longitudinal serological investigation for SBV infection at the herd level by using bulk-tank milk of a specific sheep breed from central Portugal. Materials and Methods: Bulk-tank milk samples from 68 flocks were collected in both 2015 and 2016, and lactosera were tested for IgG anti-SBV by EIA. Results and Discussion: Results show that in 2015, 92.6% (95% confidence interval [CI]: 83.9-96.8) of the bulk-tank milk samples were positive, whereas in 2016 only 77.9% (95% CI: 66.7-86.1 of the samples from the same flocks were positive. Differences in the 2015/2016 seroprevalences showed to be statistically significant (p = 0.027). This significant decrease at the herd level seems to be in agreement with reported data from other European countries and raise alerts, since increasingly favorable conditions (higher number of susceptible animals) are now present, potentially favoring SBV epidemics if improved conditions for midge replication occur in the future.


Asunto(s)
Infecciones por Bunyaviridae/veterinaria , Leche , Orthobunyavirus/aislamiento & purificación , Enfermedades de las Ovejas/virología , Animales , Infecciones por Bunyaviridae/epidemiología , Infecciones por Bunyaviridae/virología , Portugal , Estudios Seroepidemiológicos , Ovinos , Enfermedades de las Ovejas/epidemiología
5.
J Wildl Dis ; 55(1): 238-241, 2019 01.
Artículo en Inglés | MEDLINE | ID: mdl-29953315

RESUMEN

We report a case of Talaromyces marneffei skin infection in an Egyptian mongoose ( Herpestes ichneumon) in Portugal. The isolated fungus was identified through its mycologic characteristics, morphology, and PCR amplification.


Asunto(s)
Dermatomicosis/veterinaria , Herpestidae/microbiología , Talaromyces/aislamiento & purificación , Animales , Dermatomicosis/microbiología , Masculino , Portugal/epidemiología
6.
PLoS One ; 13(9): e0204624, 2018.
Artículo en Inglés | MEDLINE | ID: mdl-30261022

RESUMEN

Therapy with inhaled carbon monoxide (CO) is being tested in human clinical trials, yet the alternative use of prodrugs, CO-Releasing Molecules (CORMs), is conceptually advantageous. These molecules are designed to release carbon monoxide in specific tissues, in response to some locally expressed stimulus, where CO can trigger a cytoprotective response. The design of such prodrugs, mostly metal carbonyl complexes, must consider their ADMET profiles, including their interaction with transport plasma proteins. However, the molecular details of this interaction remain elusive. To shed light into this matter, we focused on the CORM prototype [Mo(η5-Cp)(CH2COOH)(CO)3] (ALF414) and performed a detailed molecular characterization of its interaction with bovine serum albumin (BSA), using spectroscopic and computational methods. The experimental results show that ALF414 partially quenches the intrinsic fluorescence of BSA without changing its secondary structure. The interaction between BSA and ALF414 follows a dynamic quenching mechanism, indicating that no stable complex is formed between the protein Trp residues and ALF414. The molecular dynamics simulations are in good agreement with the experimental results and confirm the dynamic and unspecific character of the interaction between ALF414 and BSA. The simulations also provide important insights into the nature of the interactions of this CORM prototype with BSA, which are dominated by hydrophobic contacts, with a contribution from hydrogen bonding. This kind of information is useful for future CORM design.


Asunto(s)
Monóxido de Carbono/metabolismo , Molibdeno/química , Molibdeno/metabolismo , Compuestos Organometálicos/química , Compuestos Organometálicos/metabolismo , Profármacos/química , Profármacos/metabolismo , Albúmina Sérica Bovina/metabolismo , Animales , Sitios de Unión , Bovinos , Dicroismo Circular , Diseño de Fármacos , Células Hep G2 , Humanos , Enlace de Hidrógeno , Interacciones Hidrofóbicas e Hidrofílicas , Técnicas In Vitro , Ratones , Simulación del Acoplamiento Molecular , Simulación de Dinámica Molecular , Molibdeno/toxicidad , Compuestos Organometálicos/toxicidad , Profármacos/toxicidad , Unión Proteica , Células RAW 264.7 , Albúmina Sérica Bovina/química , Espectrometría de Fluorescencia
7.
Vector Borne Zoonotic Dis ; 18(11): 601-604, 2018 11.
Artículo en Inglés | MEDLINE | ID: mdl-29969389

RESUMEN

INTRODUCTION: Q fever is an almost global zoonotic disease caused by Coxiella burnetii. Human infections can produce acute and chronic disease that can lead to abortions and stillbirths in pregnant women, usually infected by the inhalation of C. burnetii-contaminated aerosols or through consumption of contaminated products. Sheep are one of the primary animal reservoirs with disease being associated with vast shedding of bacteria in placentas, feces, milk, and birth fluids. Although almost neglected in the past, recent outbreaks of sheep origin have alerted the public and the scientific community. MATERIALS AND METHODS: An epidemiologic survey to estimate the seroprevalence of Q fever antibodies was performed in a representative number of sheep of all regions of continental Portugal (n = 1068), using a commercial ELISA (ID Screen Q Fever Indirect Multi-species Kit; IDvet™, Montpellier, France). RESULTS AND DISCUSSION: An anti-C. burnetii seroprevalence of 11.4% (95% confidence interval 9.6-13.5) was found, with a clear distinction between the Center region with highest seroprevalence, and the rest of the territory. Sheep traditional farming is widely present in Portugal and is part of the cultural and gastronomical background of the country. This close proximity to small ruminants may contribute to the zoonotic transfer to humans.


Asunto(s)
Anticuerpos Antibacterianos/sangre , Coxiella burnetii/inmunología , Fiebre Q/veterinaria , Enfermedades de las Ovejas/microbiología , Animales , Portugal/epidemiología , Fiebre Q/epidemiología , Fiebre Q/microbiología , Estudios Seroepidemiológicos , Ovinos , Enfermedades de las Ovejas/epidemiología , Enfermedades de las Ovejas/inmunología
8.
Transbound Emerg Dis ; 65(4): 972-975, 2018 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-29799172

RESUMEN

Q fever is a worldwide zoonotic infectious disease caused by Coxiella burnetii and sheep and goats are known to be the main reservoir for human infection. This study describes the epidemiological and laboratory findings of C. burnetii outbreaks affecting sheep and goat flocks and also provides the results of a prospective serosurvey in bulk tank milk samples to assess C. burnetii circulation in a population of sheep living in close contact to the human population in Central Portugal. In the epizooties, C. burnetii was identified in tissues of the resulting abortions by qPCR. As for the serological survey, 10.2% (95%CI: 4.5-19.2) of the 78 bulk tank milk samples collected in 2015 presented IgG antibodies against C. burnetii. The same farms were visited and sampled in 2016 and 25.6% (95%CI: 16.4-36.8) were positive. This steep increase in the number of anti-C. burnetii farms between the 2015 and 2016 collections showed to be statistically significant (p = 0.020) and is strongly suggestive of Q fever emergence in Central Portugal. Measures on animal health and on disease spread control to the human population should be considered.


Asunto(s)
Aborto Veterinario/epidemiología , Coxiella burnetii/aislamiento & purificación , Brotes de Enfermedades/veterinaria , Enfermedades de las Cabras/epidemiología , Leche/virología , Fiebre Q/epidemiología , Enfermedades de las Ovejas/epidemiología , Aborto Veterinario/virología , Animales , Anticuerpos Antibacterianos/sangre , Coxiella burnetii/inmunología , Ensayo de Inmunoadsorción Enzimática , Femenino , Enfermedades de las Cabras/virología , Cabras , Portugal/epidemiología , Embarazo , Estudios Prospectivos , Fiebre Q/veterinaria , Fiebre Q/virología , Reacción en Cadena en Tiempo Real de la Polimerasa , Ovinos , Enfermedades de las Ovejas/virología , Encuestas y Cuestionarios , Zoonosis/epidemiología
9.
J Strength Cond Res ; 31(11): 3018-3023, 2017 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-29068863

RESUMEN

Barbosa, AC, Martins, FM, Silva, AF, Coelho, AC, Intelangelo, L, and Vieira, ER. Activity of lower limb muscles during squat with and without abdominal drawing-in and Pilates breathing. J Strength Cond Res 31(11): 3018-3023, 2017-The purpose of this study was to assess the effects of abdominal drawing-in and Pilates breathing on the activity of lower limb muscles during squats. Adults (n = 13, 22 ± 3 years old) with some Pilates experience performed three 60° squats under each of the following conditions in a random order: (I) normal breathing, (II) drawing-in maneuver with normal breathing, and (III) drawing-in maneuver with Pilates breathing. Peak-normalized surface electromyography of the rectus femoris, biceps femoris, gastrocnemius medialis, and tibialis anterior during the knee flexion and extension phases of squat exercises was analyzed. There were significant differences among the conditions during the knee flexion phase for the rectus femoris (p = 0.001), biceps femoris (p = 0.038), and tibialis anterior (p = 0.001), with increasing activation from conditions I to III. For the gastrocnemius medialis, there were significant differences among the conditions during the knee extension phase (p = 0.023), with increased activity under condition I. The rectus and biceps femoris activity was higher during the extension vs. flexion phase under conditions I and II. The tibialis anterior activity was higher during the flexion compared with the extension phase under all conditions, and the medial gastrocnemius activity was higher during the extension phase under condition I. Doing squats with abdominal drawing-in and Pilates breathing resulted in increased rectus, biceps femoris, and tibialis anterior activity during the flexion phase, increasing movement stability during squat exercises.


Asunto(s)
Abdomen/fisiología , Técnicas de Ejercicio con Movimientos/métodos , Extremidad Inferior/fisiología , Músculo Esquelético/fisiología , Respiración , Adulto , Electromiografía , Femenino , Humanos , Articulación de la Rodilla/fisiología , Masculino , Músculo Cuádriceps/fisiología , Rango del Movimiento Articular
10.
J Vet Med Sci ; 79(3): 692-698, 2017 Mar 28.
Artículo en Inglés | MEDLINE | ID: mdl-28132959

RESUMEN

Paratuberculosis or Johne's disease, caused by Mycobacterium avium subsp. paratuberculosis (Map), is a chronic granulomatous enteritis affecting both domestic and wild ruminants. The present work is part of a wider set of studies designed to assess the prevalence of paratuberculosis in free ranging red deer (Cervus elaphus). With that purpose, 877 free-ranging red deer legally hunted in the Centre-eastern Portugal were submitted to necropsy and sampled for molecular methods, microbiology and histopathology. Thirty-seven (4.2%) kidneys revealed acid-fast bacilli when screened with the Ziehl-Neelsen technique. Map was detected by IS900 polymerase chain reaction (PCR) in thirty (81.1%) of the Ziehl-Neelsen positive kidneys. Subsequent PCR and/or culture from the different organs of the 37 examined animals allowed us to detect 86.4% (32 animals) infected red deer. Our results suggest that renal involvement in Map infected deer may be underdiagnosed and thus the routine examination of this organ and its inclusion in PCR techniques designed for Map detection could substantially improve the diagnostic of paratuberculosis in red deer.


Asunto(s)
Ciervos/microbiología , Riñón/microbiología , Mycobacterium avium subsp. paratuberculosis/aislamiento & purificación , Paratuberculosis/epidemiología , Animales , Animales Salvajes , Femenino , Riñón/patología , Masculino , Paratuberculosis/microbiología , Paratuberculosis/patología , Portugal/epidemiología , Prevalencia
12.
JFMS Open Rep ; 1(2): 2055116915593963, 2015.
Artículo en Inglés | MEDLINE | ID: mdl-28491367

RESUMEN

Case summary We report a clinical case of blepharitis due to Cryptococcus neoformans yeasts in a 2-year-old stray cat from northern Portugal (Vila Real) without concurrent naso-ocular signs. Ophthalmological examination revealed mucopurulent discharge from an open wound in the right upper and lower lids. Slit-lamp biomicroscopy showed a normal anterior segment, and intraocular pressure was within the normal reference interval. No fundoscopic alterations were detected in either eye by direct and indirect ophthalmoscopic examination. Cytological examination of an appositional smear showed numerous polymorphic neutrophils and macrophages, together with spherical yeast cells compatible with Cryptococcus species. Molecular analysis by means of PCR and restriction fragment length polymorphism identified C neoformans genotype VNI. The cat was treated with itraconazole, and amoxicillin and clavulanic acid, combined with a commercial ear ointment and an imidacloprid/moxidectin spot-on application for bilateral parasitic otitis caused by Otodectes cynotis. One month after treatment, the clinical signs were completely resolved. Localised cutaneous lesions, as in the present case, probably result from contamination of cat-scratch injuries with viable encapsulated yeasts. Relevance and novel information This is, to the best of our knowledge, the first clinical report of feline blepharitis due to C neoformans without concurrent naso-ocular signs. The current findings, together with those from recent reports of the infection in domestic animals, should alert the veterinary community both in Portugal and in Europe to this underdiagnosed disease.

13.
Dalton Trans ; 44(11): 5058-75, 2015 Mar 21.
Artículo en Inglés | MEDLINE | ID: mdl-25427784

RESUMEN

A few ruthenium based metal carbonyl complexes, e.g. CORM-2 and CORM-3, have therapeutic activity attributed to their ability to deliver CO to biological targets. In this work, a series of related complexes with the formula [Ru(CO)3Cl2L] (L = DMSO (3), L-H3CSO(CH2)2CH(NH2)CO2H) (6a); D,L-H3CSO(CH2)2CH(NH2)CO2H (6b); 3-NC5H4(CH2)2SO3Na (7); 4-NC5H4(CH2)2SO3Na (8); PTA (9); DAPTA (10); H3CS(CH2)2CH(OH)CO2H (11); CNCMe2CO2Me (12); CNCMeEtCO2Me (13); CN(c-C3H4)CO2Et) (14)) were designed, synthesized and studied. The effects of L on their stability, CO release profile, cytotoxicity and anti-inflammatory properties are described. The stability in aqueous solution depends on the nature of L as shown using HPLC and LC-MS studies. The isocyanide derivatives are the least stable complexes, and the S-bound methionine oxide derivative is the more stable one. The complexes do not release CO gas to the headspace, but release CO2 instead. X-ray diffraction of crystals of the model protein Hen Egg White Lysozyme soaked with 6b (4UWN) and 8 (4UWN) shows the addition of Ru(II)(CO)(H2O)4 at the His15 binding site. Soakings with 7(4UWN) produced the metallacarboxylate [Ru(COOH)(CO)(H2O)3](+) bound to the His15 site. The aqueous chemistry of these complexes is governed by the water-gas shift reaction initiated with the nucleophilic attack of HO(-) on coordinated CO. DFT calculations show this addition to be essentially barrierless. The complexes have low cytotoxicity and low hemolytic indices. Following i.v. administration of CORM-3, the in vivo bio-distribution of CO differs from that obtained with CO inhalation or with heme oxygenase stimulation. A mechanism for CO transport and delivery from these complexes is proposed.


Asunto(s)
Monóxido de Carbono/química , Portadores de Fármacos/química , Diseño de Fármacos , Compuestos Organometálicos/química , Animales , Antiinflamatorios/síntesis química , Antiinflamatorios/química , Antiinflamatorios/farmacocinética , Antiinflamatorios/farmacología , Dióxido de Carbono/química , Línea Celular , Dimetilsulfóxido/química , Portadores de Fármacos/síntesis química , Portadores de Fármacos/farmacocinética , Portadores de Fármacos/farmacología , Liberación de Fármacos , Humanos , Ratones , Modelos Moleculares , Conformación Molecular , Compuestos Organometálicos/síntesis química , Compuestos Organometálicos/farmacocinética , Compuestos Organometálicos/farmacología , Proteínas/metabolismo , Teoría Cuántica , Solubilidad , Distribución Tisular , Agua/química
14.
Angew Chem Int Ed Engl ; 54(4): 1172-5, 2015 Jan 19.
Artículo en Inglés | MEDLINE | ID: mdl-25477186

RESUMEN

We demonstrate that Ru(II)(CO)2-protein complexes, formed by the reaction of the hydrolytic decomposition products of [fac-RuCl(κ(2)-H2NCH2CO2)(CO)3] (CORM-3) with histidine residues exposed on the surface of proteins, spontaneously release CO in aqueous solution, cells, and mice. CO release was detected by mass spectrometry (MS) and confocal microscopy using a CO-responsive turn-on fluorescent probe. These findings support our hypothesis that plasma proteins act as CO carriers after in vivo administration of CORM-3. CO released from a synthetic bovine serum albumin (BSA)-Ru(II)(CO)2 complex leads to downregulation of the cytokines interleukin (IL)-6, IL-10, and tumor necrosis factor (TNF)-α in cancer cells. Finally, administration of BSA-Ru(II)(CO)2 in mice bearing a colon carcinoma tumor results in enhanced CO accumulation at the tumor. Our data suggest the use of Ru(II)(CO)2-protein complexes as viable alternatives for the safe and spatially controlled delivery of therapeutic CO in vivo.


Asunto(s)
Compuestos Organometálicos/química , Albúmina Sérica Bovina/química , Animales , Monóxido de Carbono/análisis , Monóxido de Carbono/metabolismo , Bovinos , Línea Celular Tumoral , Femenino , Células HeLa , Histidina/química , Humanos , Interleucina-10/metabolismo , Interleucina-6/metabolismo , Espectrometría de Masas , Ratones , Ratones Endogámicos BALB C , Neoplasias/tratamiento farmacológico , Profármacos/química , Profármacos/metabolismo , Profármacos/uso terapéutico , Albúmina Sérica Bovina/metabolismo , Distribución Tisular , Trasplante Heterólogo , Factor de Necrosis Tumoral alfa/metabolismo
15.
Vector Borne Zoonotic Dis ; 14(7): 531-3, 2014 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-24901256

RESUMEN

A total of 49 road-killed red foxes were used for the detection of Mycobacterium tuberculosis complex (MTC) in Portugal. MTC infection was detected by PCR in 10 red foxes (20.4%; 95% confidence interval [CI] 8.8-31.2%) and confirmed in three (6.1%; 95% CI 0.0-7.9%) of them by microbiological culture. The complex was detected in 20 tissues out of 441 by PCR techniques (4.5%; 95% CI 16.3-23.7%) and in seven tissues out of 441 (1.6%; 95% CI 4.6-9.4%) by culture. MTC was most frequently detected in the brain (8.2%) and in the mediastinal lymph nodes (8.2%). The seven cultures obtained were positive for M. bovis by PCR-based genotyping of the MTC targeting genomic deletions. This study confirms the presence of disseminated M. bovis in red foxes in Portugal, and it is the first report in the world of the natural infection in the animals' brains.


Asunto(s)
Reservorios de Enfermedades/veterinaria , Zorros/microbiología , Mycobacterium bovis/aislamiento & purificación , Tuberculosis/veterinaria , Animales , Encéfalo/microbiología , Femenino , Genotipo , Ganglios Linfáticos/microbiología , Masculino , Mycobacterium bovis/genética , Reacción en Cadena de la Polimerasa/veterinaria , Portugal/epidemiología , Tuberculosis/epidemiología
16.
Inorg Chem ; 53(5): 2652-65, 2014 Mar 03.
Artículo en Inglés | MEDLINE | ID: mdl-24520803

RESUMEN

The reaction of [MoO2Cl2(pzpy)] (1) (pzpy = 2-[3(5)-pyrazolyl]pyridine) with water in an open reflux system (16 h), in a microwave synthesis system (120 °C, 2 h), or in a Teflon-lined stainless steel digestion bomb (100 °C, 19 h) gave the molybdenum oxide/pyrazolylpyridine polymeric hybrid material [Mo3O9(pzpy)]n (2) as a microcrystalline powder in yields of 72­79%. Compound 2 can also be obtained by the hydrothermal reaction of MoO3, pzpy, and H2O at 160 °C for 3 d. Secondary products isolated from the reaction solutions included the salt (pzpyH)2(MoCl4) (3) (pzpyH = 2-[3(5)-pyrazolyl]pyridinium), containing a very rare example of the tetrahedral MoCl4(2­) anion, and the tetranuclear compound [Mo4O12(pzpy)4] (4). Reaction of 2 with excess tert-butylhydroperoxide (TBHP) led to the isolation of the oxodiperoxo complex [MoO(O2)2(pzpy)] (5). Single-crystal X-ray structures of 3 and 5 are described. Fourier transform (FT)-IR and FT Raman spectra for 1, 4, and 5 were assigned based on density functional theory calculations. The structure of 2 was determined from synchrotron powder X-ray diffraction data in combination with other physicochemical information. In 2, a hybrid organic­inorganic one-dimensional (1D) polymer, ∞(1)[Mo3O9(pzpy)], is formed by the connection of two very distinct components: a double ladder-type inorganic core reminiscent of the crystal structure of MoO3 and 1D chains of corner-sharing distorted {MoO4N2} octahedra. Compound 2 exhibits moderate activity and high selectivity when used as a (pre)catalyst for the epoxidation of cis-cyclooctene with TBHP. Under the reaction conditions used, 2 is poorly soluble and is gradually converted into 5, which is at least partly responsible for the catalytic reaction.

17.
J Biomed Opt ; 18(9): 095004, 2013 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-24077666

RESUMEN

We evaluate the biological and physicochemical effects of a Fusarium oxysporum crude extract (CE) on the skin of healthy rats. The CE is topically applied and subsequently the skin is collected after 3, 6, 12, and 24 h. The samples are analyzed by Fourier transform infrared photoacoustic spectroscopy (FTIR-PAS) and histomorphometric analysis. Terminal dUTP nick end labeling (TUNEL assay) is performed to detect both the cells in apoptosis and proliferation. There is a thickening of the epidermis after 6, 12, and 24 h and dermis after 12 and 24 h of CE application. A reduction of the dermis thickness is observed at 3 and 6 h. The treated skin shows higher labeling intensity by TUNEL at 3 h, while a higher intensity by proliferating cell nuclear antigen occurs at 3 and 12 h. FTIR-PAS data support the histology observations showing an increase in the absorption peaks in the dermis after the application of the CE. F. oxysporum CE permeated through the epidermis and the dermis, reaching the subcutaneous tissue, inducing cell apoptosis, and causing physicochemical changes in the organic molecules located in the dermis. This is the first known study associating histopathological and physical chemistry changes on healthy skin after the application of F. oxysporum CE.


Asunto(s)
Apoptosis/efectos de los fármacos , Mezclas Complejas/farmacología , Fusarium/química , Piel/efectos de los fármacos , Animales , Colágeno/análisis , Colágeno/química , Etiquetado Corte-Fin in Situ , Masculino , Técnicas Fotoacústicas , Fotomicrografía , Ratas , Ratas Wistar , Piel/citología , Piel/patología , Espectroscopía Infrarroja por Transformada de Fourier , Estadísticas no Paramétricas
18.
Dalton Trans ; 42(17): 5985-98, 2013 May 07.
Artículo en Inglés | MEDLINE | ID: mdl-23223860

RESUMEN

The complex fac-[Mo(CO)(3)(histidinate)]Na has been reported to be an effective CO-Releasing Molecule in vivo, eliciting therapeutic effects in several animal models of disease. The CO releasing profile of this complex in different settings both in vitro and in vivo reveals that the compound can readily liberate all of its three CO equivalents under biological conditions. The compound has low toxicity and cytotoxicity and is not hemolytic. CO release is accompanied by a decrease in arterial blood pressure following administration in vivo. We studied its behavior in solution and upon the interaction with proteins. Reactive oxygen species (ROS) generation upon exposure to air and polyoxomolybdate formation in soaks with lysozyme crystals were observed as processes ensuing from the decomposition of the complex and the release of CO.


Asunto(s)
Monóxido de Carbono/metabolismo , Complejos de Coordinación/química , Compuestos Organometálicos/química , Profármacos/química , Animales , Sitios de Unión , Línea Celular , Supervivencia Celular/efectos de los fármacos , Complejos de Coordinación/síntesis química , Complejos de Coordinación/toxicidad , Cristalografía por Rayos X , Hemodinámica , Hemoglobinas/química , Hemoglobinas/metabolismo , Hemólisis , Células Hep G2 , Humanos , Ratones , Muramidasa/química , Muramidasa/metabolismo , Compuestos Organometálicos/síntesis química , Compuestos Organometálicos/toxicidad , Profármacos/síntesis química , Profármacos/toxicidad , Estructura Terciaria de Proteína , Albúmina Sérica/química , Albúmina Sérica/metabolismo
19.
Accid Anal Prev ; 47: 11-5, 2012 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-22405233

RESUMEN

Health care workers are attributed to the group at highest risk of occupationally acquired bloodborne diseases as the result of contact with blood and body fluids. A cross sectional study was conducted between November 2009 and February 2010 in the North of Portugal, to identify potential risk factors for needlestick and sharps injuries. A questionnaire was provided to 363 health care professionals. Logistic regression was used to identify risk factors associated to needlestick and sharps injuries, calculating odds ratio (OR) and their 95% confidence interval (CI). Sixty-five percent of health care workers (64.5%, 234/363) reported needlestick and sharps injuries in the previous 5 years. Of the injured workers, 74.8% were nurses. Of the total injuries reported, the commonest were from syringe needle unit. The multivariate logistic regression model showed that the strongest risk factor was having more than 10 years or more of work in health services (OR 3.37, 95% CI 1.82, 6.24). Another significantly related factor was being over 39 years-old (OR 1.94, 95% CI 1.03, 3.63). In Portugal, there is a lack of epidemiological evidence related to needlestick and sharps injuries. Considering that patients infected with hepatitis B and C virus are commonly encountered in the hospital environment and that the prevalence of HIV infection in Portugal is one of the highest in Europe, these results should be considered in the design of biosafety strategies at the Hospital Center.


Asunto(s)
Lesiones por Pinchazo de Aguja/epidemiología , Traumatismos Ocupacionales/epidemiología , Personal de Hospital/estadística & datos numéricos , Factores de Edad , Competencia Clínica , Estudios Transversales , Femenino , Humanos , Masculino , Persona de Mediana Edad , Portugal , Factores de Riesgo , Factores de Tiempo , Adulto Joven
20.
Inorg Chem ; 50(2): 525-38, 2011 Jan 17.
Artículo en Inglés | MEDLINE | ID: mdl-21141938

RESUMEN

The dioxomolybdenum(VI) complexes [MoO2Cl2(PzPy)] (1) and [MoO2(OSiPh3)2(PzPy)] (5) (PzPy = 2-[3(5)-pyrazolyl]pyridine) were synthesized and characterized by vibrational spectroscopy, with assignments being supported by DFT calculations. Complex 5 was additionally characterized by single crystal X-ray diffraction. Recrystallization of 1 under different conditions originated crystal structures containing either the mononuclear [MoO2Cl2(PzPy)] complex co-crystallized with 2-[3(5)-pyrazolyl]pyridinium chloride, binuclear [Mo2O4(µ2-O)Cl2(PzPy)2] complexes, or the oxodiperoxomolybdenum(VI) complex [MoO(O2)2Cl(PzPyH)], in which a 2-[3(5)-pyrazolyl]pyridinium cation weakly interacts with the Mo(VI) center via a pyrazolyl N-atom. The crystal packing in the different structures is mediated by a variety of supramolecular interactions: hydrogen bonding involving the pyridinium and/or pyrazolyl N-H groups, weak CH · · · O and CH · · · π contacts, and strong π-π stacking. Complexes 1 and 5 are moderately active catalysts for the epoxidation of cis-cyclooctene at 55 °C using tert-butylhydroperoxide as oxidant, giving 1,2-epoxycyclooctane as the only reaction product. Insoluble materials were recovered at the end of the first catalytic runs and characterized by IR spectroscopy, elemental analysis, scanning electron microscopy (SEM)-energy dispersive spectroscopy (EDS), and powder X-ray diffraction. For complex 5 the loss of the triphenylsiloxy ligands during the catalytic run resulted in the formation of a tetranuclear complex, [Mo4O8(µ2-O)4(PzPy)4]. The recovered solids could be used as efficient heterogeneous catalysts for the epoxidation of cyclooctene, showing no loss of catalytic performance between successive catalytic runs.

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