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Although focused interests are often associated with a diagnosis of autism, they are common in nonautistic individuals as well. Previous studies have explored how these interests impact cognitive, social, and language development. While some research has suggested that strong interests can detract from learning (particularly for autistic children), newer research has indicated that they can be advantageous. In this pre-registered study, we asked whether focused interests support word learning in 44 autistic children and a vocabulary-matched sample of 44 nonautistic children (mean ages 58 and 34 months respectively). In a word-learning task administered over Zoom, children were exposed to an action labeled by a novel word. The action was either depicted by their focused interest or by a neutral image; stimuli were personalized for each child. At test, they were asked to identify the referent of the novel word, and their eye gaze was evaluated as a measure of learning. The preregistered analyses revealed an effect of focused interests, and post-hoc analyses clarified that autistic children learned the novel word in both the focused interest and neutral conditions, while nonautistic children only showed evidence of learning in the neutral condition. These results suggest that focused interests are not disruptive for vocabulary learning in autism, and thus they could be utilized in programming that supports early language learning in this population.
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Trastorno Autístico , Vocabulario , Humanos , Masculino , Femenino , Preescolar , Desarrollo del Lenguaje , Aprendizaje Verbal/fisiología , Niño , Aprendizaje/fisiologíaRESUMEN
Carbon-Fibre-Reinforced Polymers (CFRPs) have seen a steady rise in modern industrial applications due to their high strength-to-weight ratio and corrosion resistance. However, their potential is being hindered by delamination which is induced on them during machining operations. This has led to the adoption of new and innovative techniques like cryogenic-assisted machining which could potentially help reduce delamination. This study is aimed at investigating the effect of cryogenic conditions on achieving better hole quality with reduced delamination. In this paper, the numerical analysis of the drilling of CFRP composites is presented. Drilling tests were performed experimentally for validation purposes. The effects of cooling conditions and their subsequent effect on the thrust force and delamination were evaluated using ABAQUS/CAE. The numerical models and experimental results both demonstrated a significant reduction in the delamination factor in CFRP under cryogenic drilling conditions.
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The ever-increasing demand for materials to have superior properties and satisfy functions in the field of soft robotics and beyond has resulted in the advent of the new field of four-dimensional (4D) printing. The ability of these materials to respond to various stimuli inspires novel applications and opens several research possibilities. In this work, we report on the 4D printing of one such Shape Memory Polymer (SMP) tBA-co-DEGDA (tert-Butyl Acrylate with diethylene glycol diacrylate). The novelty lies in establishing the relationship between the various characteristic properties (tensile stress, surface roughness, recovery time, strain fixity, and glass transition temperature) concerning the fact that the print parameters of the laser pulse frequency and print speed are governed in the micro-stereolithography (Micro SLA) method. It is found that the sample printed with a speed of 90 mm/s and 110 pulses/s possessed the best batch of properties, with shape fixity percentages of about 86.3% and recovery times as low as 6.95 s. The samples built using the optimal parameters are further subjected to the addition of graphene nanoparticles, which further enhances all the mechanical and surface properties. It has been observed that the addition of 0.3 wt.% of graphene nanoparticles provides the best results.
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Additive manufacturing (AM) is replacing conventional manufacturing techniques due to its ability to manufacture complex structures with near-net shape and reduced material wastage. However, the poor surface integrity of the AM parts deteriorates the service life of the components. The AM parts should be subjected to post-processing treatment for improving surface integrity and fatigue life. In this research, maraging steel is printed using direct metal laser sintering (DMLS) process and the influence of grinding on the fatigue life of this additively manufactured material was investigated. For this purpose, the grinding experiments were performed under two different grinding environments such as dry and cryogenic conditions using a cubic boron nitride (CBN) grinding wheel. The results revealed that surface roughness could be reduced by about 87% under cryogenic condition over dry grinding. The fatigue tests carried out on the additive manufactured materials exposed a substantial increase of about 170% in their fatigue life when subjected to cryogenic grinding.
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Biophysical interaction of amphiphilic fluorescent surfactant-ruthenium(II) complexes and its precursor ruthenium(II) complexes with drug carrying proteins such as bovine and human serum albumins (BSA and HSA) have been studied through the UV-visible absorption, fluorescence and circular dichroism spectroscopic techniques to correlate the impact of head and tail groups of the metallosurfactants towards the designing of metallodrugs for the biomedical applications. The obtained results showed that both precursor- and surfactant-ruthenium(II) complexes interact with BSA/HSA via ground state protein-complex formation and their quenching follows the static mechanism. The extent of protein quenching and binding parameters resulted that the surfactant-ruthenium(II) complexes effectively interact with protein compared to their precursor-ruthenium(II) complexes, and also those interaction have greatly influenced by the change in the head group size compared to change in the tail group length. Interestingly on increasing the temperature, the protein-complex binding strength was decreased for the precursor-ruthenium(II) complexes, those increased for the surfactant-ruthenium(II) complexes, probably due to the respective involvement of electrostatic and hydrophobic interactions as supported by the thermodynamics of protein-complex interaction. Moreover, the results from UV-visible, synchronous and circular dichroism studies confirmed the occurrence of conformational and micro environmental changes in BSA/HSA upon binding with these complexes. It is also noted that HSA has more binding affinity with surfactant-ruthenium(II) complexes compared to BSA. The free radical scavenging ability against DPPH, ABTS, NO and superoxide free radical assays suggested that surfactant-ruthenium(II) complexes have better free radical scavenging ability compared to precursor-ruthenium(II) complexes.Communicated by Ramaswamy H. Sarma.
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Rutenio , Animales , Antioxidantes , Sitios de Unión , Bovinos , Dicroismo Circular , Humanos , Unión Proteica , Albúmina Sérica Bovina/metabolismo , Espectrometría de Fluorescencia , Tensoactivos , TermodinámicaRESUMEN
Despite the remarkable evolutionary success of insects at colonizing every conceivable terrestrial and aquatic habitat, only five Halobates (Heteroptera: Gerridae) species (~0.0001% of all known insect species) have succeeded at colonizing the open ocean - the largest biome on Earth. This remarkable evolutionary achievement likely required unique adaptations for them to survive and thrive in the challenging oceanic environment. For the first time, we explore the morphology and behavior of an open-ocean Halobates germanus and a related coastal species H. hayanus to understand mechanisms of these adaptations. We provide direct experimental evidence based on high-speed videos which reveal that Halobates exploit their specialized and self-groomed body hair to achieve extreme water repellence, which facilitates rapid skating and plastron respiration under water. Moreover, the grooming behavior and presence of cuticular wax aids in the maintenance of superhydrophobicity. Further, reductions of their body mass and size enable them to achieve impressive accelerations (~400 ms-2) and reaction times (~12 ms) to escape approaching predators or environmental threats and are crucial to their survival under harsh marine conditions. These findings might also inspire rational strategies for developing liquid-repellent surfaces for drag reduction, water desalination, and preventing bio-fouling.
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Evolución Biológica , Tamaño Corporal , Ecosistema , Heterópteros , Animales , Conducta Animal , Heterópteros/anatomía & histología , Heterópteros/ultraestructura , Océanos y MaresRESUMEN
INTRODUCTION: The adverse health effects associated with exposure to traffic-related air pollutants (TRAPs) remain a key public health issue. Often, exposure assessments have not represented the small-scale variation and elevated concentrations found near major roads and in urban settings. This research explores approaches aimed at improving exposure estimates of TRAPs that can reduce exposure measurement error when used in health studies. We consider dispersion models designed specifically for the near-road environment, as well as spatiotemporal and data fusion models. These approaches are implemented and evaluated utilizing data collected in recent modeling, monitoring, and epidemiological studies conducted in Detroit, Michigan. APPROACH: Dispersion models, which estimate near-road pollutant concentrations and individual exposures based on first principles - and in particular, high fidelity models - can provide great flexibility and theoretical strength. They can represent the spatial variability of TRAP concentrations at locations not measured by conventional and spatially sparse air quality monitoring networks. A number of enhancements to dispersion modeling and mobile on-road emissions inventories were considered, including the representation of link-based road networks and updated estimates of temporal allocation of traffic activity, emission factors, and meteorological inputs. The recently developed Research LINE-source model (RLINE), a Gaussian line-source dispersion model specifically designed for the near-road environment, was used in an operational evaluation that compared predicted concentrations of nitrogen oxides (NOx), carbon monoxide (CO), and PM2.5 (particulate matter ≤ 2.5 µm in aerodynamic diameter) with observed concentrations at air quality monitoring stations located near high-traffic roads. Spatiotemporal and data fusion models provided additional and complementary approaches for estimating TRAP exposures. We formulated both nonstationary universal kriging models that exploit the spatial correlation in the monitoring data, and data fusion models that leverage the information contained in both the monitoring data and the output of numerical models, specifically RLINE. These models were evaluated using observations of nitric oxide (NO), NOx, black carbon (BC), and PM2.5 monitored along transects crossing major roads in Detroit. We also examined model assumptions, including the appropriateness of the covariance functions, errors in RLINE outputs, and the effects of jointly modeling two pollutants and using an updated emission inventory. RESULTS: For CO and NOx, dispersion model performance was best when monitoring sites were close to major roads, during downwind conditions, during weekdays, and during certain seasons. The ability to discern local and particularly the traffic-related portion of PM2.5 was limited, a result of high background levels, the sparseness of the monitoring network, and large uncertainties for certain sources (e.g., area, fugitive) and some processes (e.g., formation of secondary aerosols). Sensitivity analyses of alternative meteorological inputs and updated emission factors showed some performance gain when using local (on-site) meteorological data and updated inventories. Overall, the operational evaluation suggested RLINE's usefulness for estimating spatially and temporally resolved exposure estimates. The application of the universal kriging models confirmed that wind speed and direction are important drivers of nonstationarity in pollutant concentrations, and that these models can predict exposure estimates that have lower prediction errors than do stationary model counterparts. The application of the Bayesian data fusion models suggested that the RLINE output had a spatially varying additive bias for NOx and PM2.5 and provided little additional information for NOx, besides what is already contained in traffic and geographical information system (GIS) covariates, but had improved estimates of PM2.5 concentrations. Results of the nonstationary Bayesian data fusion model that used RLINE output across a field spanning the measurement sites were similar to a regression-based Bayesian data fusion approach that used only RLINE output at the monitoring locations, with the latter being computationally less burdensome. Using the regression-based Bayesian data fusion model, we found that RLINE with the updated emission inventory provided results that were more useful for estimating NOx concentration at unmonitored sites, but the updated emission inventory did not improve predictions of PM2.5 concentrations. Joint modeling of NOx and PM2.5 was not useful, a result of differences in RLINE's utility in predicting PM2.5 and NOx - useful for the former, but not for the latter - and differences in the spatial dependence structures of the two pollutants. Overall, information provided by RLINE was shown to have the potential to improve spatiotemporal estimates of TRAP concentrations. CONCLUSIONS: The study results should be interpreted and generalized cautiously given the limitations of the data used. Similar analyses in other settings are recommended for confirming and extending our findings. Still, the study highlights considerations that are relevant for exposure estimates used in health studies. The ability of a dispersion model to accurately reproduce and predict a pollutant depends on the pollutant as well as on spatial and temporal factors, such as the distance and direction from the road, time-of-day, and day-of-week. The nature and source of exposure measurement errors should be taken into consideration, particularly in health studies that take advantage of time- activity information that describes where and when individuals are exposed to pollution. Efforts to refine model inputs and improve model performance can be helpful; meteorological inputs may be the most critical. For both dispersion and spatiotemporal statistical models, sufficient and high-quality monitoring data are essential for developing and evaluating these models. Our analyses using Bayesian data fusion models confirm the presence of spatially varying errors in dispersion model outputs and allow quantification of both the magnitude and the spatial nature of these errors. This valuable information can be leveraged in health studies examining air pollution exposure as well as in studies informing regulatory responses.
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Contaminantes Atmosféricos/análisis , Teorema de Bayes , Monitoreo del Ambiente/métodos , Modelos Estadísticos , Emisiones de Vehículos/análisis , Carbono/análisis , Monóxido de Carbono/análisis , Sistemas de Información Geográfica , Humanos , Óxidos de Nitrógeno/análisisRESUMEN
Magnetic resonance elastography (MRE) is increasingly being applied to thin or small structures in which wave propagation is dominated by waveguide effects, which can substantially bias stiffness results with common processing approaches. The purpose of this work was to investigate the importance of such biases and artifacts on MRE inversion results in: (i) various idealized 2D and 3D geometries with one or more dimensions that are small relative to the shear wavelength; and (ii) a realistic cardiac geometry. Finite element models were created using simple 2D geometries as well as a simplified and a realistic 3D cardiac geometry, and simulated displacements acquired by MRE from harmonic excitations from 60 to 220 Hz across a range of frequencies. The displacement wave fields were inverted with direct inversion of the Helmholtz equation with and without the application of bandpass filtering and/or the curl operator to the displacement field. In all geometries considered, and at all frequencies considered, strong biases and artifacts were present in inversion results when the curl operator was not applied. Bandpass filtering without the curl was not sufficient to yield accurate recovery. In the 3D geometries, strong biases and artifacts were present in 2D inversions even when the curl was applied, while only 3D inversions with application of the curl yielded accurate recovery of the complex shear modulus. These results establish that taking the curl of the wave field and performing a full 3D inversion are both necessary steps for accurate estimation of the shear modulus both in simple thin-walled or small structures and in a realistic cardiac geometry when using simple inversions that neglect the hydrostatic pressure term. In practice, sufficient wave amplitude, signal-to-noise ratio, and resolution will be required to achieve accurate results.
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Analysis of biomedical signals can yield invaluable information for prognosis, diagnosis, therapy evaluation, risk assessment, and disease prevention which is often recorded as short time series data that challenges existing complexity classification algorithms such as Shannon entropy (SE) and other techniques. The purpose of this study was to improve previously developed multiscale entropy (MSE) technique by incorporating nearest-neighbor moving-average kernel, which can be used for analysis of nonlinear and non-stationary short time series physiological data. The approach was tested for robustness with respect to noise analysis using simulated sinusoidal and ECG waveforms. Feasibility of MSE to discriminate between normal sinus rhythm (NSR) and atrial fibrillation (AF) was tested on a single-lead ECG. In addition, the MSE algorithm was applied to identify pivot points of rotors that were induced in ex vivo isolated rabbit hearts. The improved MSE technique robustly estimated the complexity of the signal compared to that of SE with various noises, discriminated NSR and AF on single-lead ECG, and precisely identified the pivot points of ex vivo rotors by providing better contrast between the rotor core and the peripheral region. The improved MSE technique can provide efficient complexity analysis of variety of nonlinear and nonstationary short-time biomedical signals.
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Electrocardiografía/métodos , Procesamiento de Señales Asistido por Computador , Algoritmos , Animales , Fibrilación Atrial/fisiopatología , Entropía , Corazón/fisiología , ConejosRESUMEN
PURPOSE: Atrial fibrillation (AF) is the most common sustained cardiac arrhythmia that causes stroke affecting more than 2.3 million people in the US and is increasing in prevalence due to ageing population causing a new global epidemic. Catheter ablation with pulmonary vein isolation (PVI) to terminate AF is successful for paroxysmal AF but suffers limitations with persistent AF patients as current mapping methods cannot identify AF active substrates outside of PVI region. Recent evidences in the mechanistic understating of AF pathophysiology suggest that ectopic activity, localized re-entrant circuit with fibrillatory propagation and multiple circuit re-entries may all be involved in human AF. The authors developed novel electrogram analysis methods and validated using optical mapping data from isolated rabbit hearts to accurately identify rotor pivot points. The purpose of this study was to assess the feasibility of generating patient-specific 3D maps for intraprocedural guidance for catheter ablation using intracardiac electrograms from a persistent AF patient using novel electrogram analysis methods. METHODS: A persistent AF patient with clinical appointment for AF ablation was recruited for this study with IRB approval. 1055 electrograms throughout the left and right atrium were obtained for offline analysis with the novel approaches such as multiscale entropy, multiscale frequency, recurrence period density entropy, kurtosis and empirical mode decomposition to generate patient specific 3D maps. 3D Shannon Entropy, Renyi Entropy and Dominant frequency maps were also generated for comparison purposes along with local activation time and complex fractionated electrogram analysis maps. RESULTS: Patient specific 3D maps were obtained for each of the different approach. The 3D maps indicate potential active sites outside the PVI region. However, presence of rotors cannot be confirmed and validation of these approaches is required on a larger dataset. CONCLUSIONS: Conventional catheter mapping system can be used for generating patient specific 3D maps with short time series analysis using the novel approaches.
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Aviation is a unique anthropogenic source with four-dimensional varying emissions, peaking at cruise altitudes (9-12 km). Aircraft emission budgets in the upper troposphere lower stratosphere region and their potential impacts on upper troposphere and surface air quality are not well understood. Our key objective is to use chemical transport models (with prescribed meteorology) to predict aircraft emissions impacts on the troposphere and surface air quality. We quantified the importance of including full-flight intercontinental emissions and increased horizontal grid resolution. The full-flight aviation emissions in the Northern Hemisphere contributed ~1.3% (mean, min-max: 0.46, 0.3-0.5 ppbv) and 0.2% (0.013, 0.004-0.02 µg/m3) of total O3 and PM2.5 concentrations at the surface, with Europe showing slightly higher impacts (1.9% (O3 0.69, 0.5-0.85 ppbv) and 0.5% (PM2.5 0.03, 0.01-0.05 µg/m3)) than North America (NA) and East Asia. We computed seasonal aviation-attributable mass flux vertical profiles and aviation perturbations along isentropic surfaces to quantify the transport of cruise altitude emissions at the hemispheric scale. The comparison of coarse (108 × 108 km2) and fine (36 × 36 km2) grid resolutions in NA showed ~70 times and ~13 times higher aviation impacts for O3 and PM2.5 in coarser domain. These differences are mainly due to the inability of the coarse resolution simulation to capture nonlinearities in chemical processes near airport locations and other urban areas. Future global studies quantifying aircraft contributions should consider model resolution and perhaps use finer scales near major aviation source regions.
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The interaction of surfactant-cobalt(III) complexes [Co(bpy)(dien)TA](ClO4)3 · 3H2O (1) and [Co(dien)(phen)TA](ClO4)3 · 4H2O (2), where bpy = 2,2'-bipyridine, dien = diethylenetriamine, phen = 1,10-phenanthroline and TA = tetradecylamine with human serum albumin (HSA) under physiological conditions was analyzed using steady state, synchronous, 3D fluorescence, UV/visabsorption and circular dichroism spectroscopic techniques. The results show that these complexes cause the fluorescence quenching of HSA through a static mechanism. The binding constant (Kb ) and number of binding-sites (n) were obtained at different temperatures. The corresponding thermodynamic parameters (∆G°, ∆H° and ∆S°) and Ea were also obtained. According to Förster's non-radiation energy transfer theory, the binding distance (r) between the complexes and HSA were calculated. The results of synchronous and 3D fluorescence spectroscopy indicate that the binding process has changed considerably the polarity around the fluorophores, along with changes in the conformation of the protein. The antimicrobial and anticancer activities of the complexes were tested and the results show that the complexes have good activities against pathogenic microorganisms and cancer cells.
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Cobalto/química , Compuestos Organometálicos/química , Albúmina Sérica/química , Tensoactivos/química , Sitios de Unión , Muerte Celular/efectos de los fármacos , Relación Dosis-Respuesta a Droga , Humanos , Células Jurkat , Estructura Molecular , Compuestos Organometálicos/farmacología , Relación Estructura-Actividad , TermodinámicaRESUMEN
The polymer-cobalt(III) complexes, [Co(bpy)(dien)BPEI]Cl3 · 4H2O (bpy = 2,2'-bipyridine, dien = diethylentriamine, BPEI = branched polyethyleneimine) were synthesized and characterized. The interaction of these complexes with human serum albumin (HSA) and bovine serum albumin (BSA) was investigated under physiological conditions using various physico-chemical techniques. The results reveal that the fluorescence quenching of serum albumins by polymer-cobalt(III) complexes took place through static quenching. The binding of these complexes changed the molecular conformation of the protein considerably. The polymer-cobalt(III) complex with x = 0.365 shows antimicrobial activity against several human pathogens. This complex also induces cytotoxicity against MCF-7 through apoptotic induction. However, further studies are needed to decipher the molecular mode of action of polymer-cobalt(III) complex and for its possible utilization in anticancer therapy.
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Antibacterianos/farmacología , Antifúngicos/farmacología , Bacterias/efectos de los fármacos , Hongos/efectos de los fármacos , Compuestos Organometálicos/farmacología , Albúmina Sérica/química , Animales , Antibacterianos/síntesis química , Antibacterianos/química , Antifúngicos/síntesis química , Antifúngicos/química , Apoptosis/efectos de los fármacos , Sitios de Unión , Bovinos , Proliferación Celular/efectos de los fármacos , Cobalto/química , Cobalto/farmacología , Relación Dosis-Respuesta a Droga , Ensayos de Selección de Medicamentos Antitumorales , Humanos , Células MCF-7 , Pruebas de Sensibilidad Microbiana , Estructura Molecular , Compuestos Organometálicos/síntesis química , Compuestos Organometálicos/química , Polímeros/química , Polímeros/farmacología , Relación Estructura-ActividadRESUMEN
The comparative binding effect of single and double aliphatic chain containing surfactant-cobalt(III) complexes cis-[Co(bpy)2(DA)2](ClO4)3·2H2O (1), cis-[Co(bpy)2(DA)Cl](ClO4)2·2H2O (2), cis-[Co(phen)2(CA)2](ClO4)3·2H2O (3), and cis-[Co(phen)2(CA)Cl](ClO4)2·2H2O (4) with bovine serum albumin (BSA) under physiological condition was analyzed by steady state, time resolved fluorescence, synchronous, three-dimensional fluorescence, UV-Visible absorption and circular dichroism spectroscopic techniques. The results show that these complexes cause the fluorescence quenching of BSA through a static mechanism. The binding constants (Kb) and the number of binding sites were calculated and binding constant values are found in the range of 10(4)-10(5) M(-1). The results indicate that compared to single chain complex, double chain surfactant-cobalt(III) complex interacts strongly with BSA. Also the sign of thermodynamic parameters (ΔG°, ΔH°, and ΔS°) indicate that all the complexes interact with BSA through hydrophobic force. The binding distance (r) between complexes and BSA was calculated using Förster non-radiation energy transfer theory and found to be less than 7 nm. The results of synchronous, three dimensional fluorescence and circular dichroism spectroscopic methods indicate that the double chain surfactant-cobalt(III) complexes changed the conformation of the protein considerably than the respective single chain surfactant-cobalt(III) complexes. Antimicrobial studies of the complexes showed good activities against pathogenic microorganisms.
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Cobalto/metabolismo , Albúmina Sérica Bovina/metabolismo , Tensoactivos/metabolismo , Animales , Antiinfecciosos/farmacología , Bacterias/efectos de los fármacos , Sitios de Unión , Bovinos , Dicroismo Circular , Cobalto/farmacología , Complejos de Coordinación/metabolismo , Complejos de Coordinación/farmacología , Transferencia de Energía/efectos de los fármacos , Hongos/efectos de los fármacos , Micelas , Pruebas de Sensibilidad Microbiana , Unión Proteica/efectos de los fármacos , Albúmina Sérica Bovina/química , Espectrometría de Fluorescencia , Espectrofotometría Ultravioleta , Termodinámica , Triptófano/metabolismo , Tirosina/metabolismoRESUMEN
The characteristics of the binding reaction of surfactant-cobalt(III) complex, cis-[Co(phen)2(C14H29NH2)]Cl2·3H2O (phen=1,10-phenanthroline, C14H29NH2=tetradecylamine) with human serum albumin (HSA) were studied by fluorescence and UV-vis absorption spectroscopy. In addition, the effect of the surfactant-cobalt(III) complex on the conformation of HSA was analysed using synchronous fluorescence spectroscopy. The experimental results showed that surfactant-cobalt(III) complex caused the fluorescence quenching of HSA through a combination of static and dynamic quenching. The number of binding sites (n) and apparent binding constant (K(a)) of surfactant-cobalt(III) complex (above and below the critical micelle concentration (cmc) were determined at various temperatures. According to the thermodynamic parameters, it is likely that hydrophobic interactions are involved in the binding process. The cancer chemotherapeutic potential of surfactant-cobalt(III) complex on ME-180 cervical cancer cell was determined using MTT assay and specific staining techniques. The complex affected the viability of the cells significantly and the cells succumbed through an apoptosis process as seen in the nuclear morphology and cytoplasmic features. In addition, single-cell electrophoresis indicated DNA damage.
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Antineoplásicos/química , Antineoplásicos/farmacocinética , Cobalto/química , Fenantrolinas/química , Albúmina Sérica/química , Tensoactivos/química , Apoptosis/efectos de los fármacos , Línea Celular Tumoral , Humanos , Estructura Molecular , Espectrometría de FluorescenciaRESUMEN
A new Ru(III) Schiff base complexes of the type [RuX(EPh(3))L] (X = Cl/Br; E = P/As; L = dianion of the Schiff bases were derived by the condensation of 1,4-diformylbenzene with o-aminobenzoic acid/o-aminophenol/o-aminothiophenol in the 1:2 stoichiometric ratio) have been synthesized from the reactions of [RuX(3)(EPh(3))(3)] with appropriate Schiff base ligands in benzene in the 2:1 stoichiometric ratio. The new complexes have been characterized by analytical, spectral (IR, electronic, (1)H, (13)C NMR and ESR), magnetic moment and electrochemical studies. An octahedral structure has been tentatively proposed for all these new complexes. All the new complexes have been found to be better catalyst for the oxidation of alcohols using molecular oxygen as co-oxidant at ambient temperature and aryl-aryl coupling reactions. These complexes were also subjected to antibacterial activity studies against Escherichia coli, Aeromonas hydrophilla and Salmonella typhi.
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Antibacterianos/química , Antibacterianos/farmacología , Rutenio/química , Rutenio/farmacología , Bases de Schiff/química , Bases de Schiff/farmacología , Aeromonas hydrophila/efectos de los fármacos , Antibacterianos/síntesis química , Arsenicales/química , Bromuros/química , Cloruros/química , Electroquímica , Escherichia coli/efectos de los fármacos , Pruebas de Sensibilidad Microbiana , Compuestos Organofosforados/química , Oxidación-Reducción/efectos de los fármacos , Salmonella typhi/efectos de los fármacos , Bases de Schiff/síntesis química , Análisis EspectralRESUMEN
An octahedral ruthenium(III) Schiff base complexes of the type [RuX(EPh(3))(L)] (where, X=Cl/Br; E=As/P; L=dianion of the Schiff bases derived from acetoacetanilide with o-phenylenediamine and salicylaldehyde/o-hydroxyacetophenone/o-vanillin/2-hydroxy-1-naphthaldehyde) have been synthesized from the reactions of equimolar reactions of [RuX(3)(EPh(3))(3)] and Schiff bases in benzene. The new Ru(III) Schiff base complexes have been characterized by elemental analyses, FT-IR, electronic, (1)H NMR and (13)C NMR spectra, EPR spectral studies, powder X-ray diffraction (XRD) and electrochemical studies. The new complexes were found to be effective catalysts for aryl-aryl coupling and the oxidation of alcohols into their corresponding carbonyl compounds, respectively, using molecular oxygen atmosphere at ambient temperature. Further, the new Ru(III) Schiff base complexes were screened for their antibacterial activity against Pseudomonas aeruginosa, Vibrio cholera, Salomonella typhi and Staphylococcus aureaus.
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Antibacterianos/química , Rutenio/química , Bases de Schiff/química , Bases de Schiff/farmacología , Espectrofotometría/métodos , Antibacterianos/síntesis química , Antibacterianos/farmacología , Benceno/química , Catálisis , Electricidad , Electroquímica , Espectroscopía de Resonancia por Spin del Electrón , Espectroscopía de Resonancia Magnética , Pruebas de Sensibilidad Microbiana , Estructura Molecular , Oxidación-Reducción , Polvos , Pseudomonas aeruginosa/efectos de los fármacos , Salmonella typhi/efectos de los fármacos , Bases de Schiff/síntesis química , Espectroscopía Infrarroja por Transformada de Fourier , Staphylococcus aureus/efectos de los fármacos , Vibrio cholerae/efectos de los fármacos , Difracción de Rayos XRESUMEN
We have previously reported on calcium transport mechanisms in American lobster, Homarus americanus, using (45)Ca(2+) coupled with vesicle preparations of hepatopancreatic endoplasmic reticulum. The active transport of calcium across membranes bordering calcium-sequestering stores such as sarcoplasmic or endoplasmic reticulum is catalyzed by membrane-spanning proteins, the sarco-endoplasmic Ca(2+)-ATPases (SERCAs). In the study described here we used advanced bioinformatics and molecular techniques to clone SERCA from the economically important Caribbean spiny lobster, Panulirus argus. We report the complete cloning of a full-length SERCA from P. argus antenna cDNA (GenBank accession number AY702617). This cDNA has a 1020-amino acid residue open reading frame which is 90% identical to published sequences of other crustacean SERCA proteins. Our data support the hypothesis that one crustacean and three vertebrate genes controlling calcium transport were derived from a common ancestral gene.
Asunto(s)
Calcio/metabolismo , Retículo Endoplásmico/enzimología , Palinuridae/enzimología , Filogenia , ATPasas Transportadoras de Calcio del Retículo Sarcoplásmico/genética , Animales , Secuencia de Bases , Transporte Biológico Activo/fisiología , Clonación Molecular , Análisis por Conglomerados , Biología Computacional , Cartilla de ADN/genética , ADN Complementario/genética , Hibridación in Situ , Datos de Secuencia Molecular , Palinuridae/genética , Reacción en Cadena de la Polimerasa de Transcriptasa Inversa , Análisis de Secuencia de ADNRESUMEN
A new class of surfactant-cobalt(III) complexes, cis-[Co(bpy)(2)(C(11)H(23)NH(2))Cl](2+) (1) and cis-[Co(phen)(2)(C(11)H(23)NH(2))Cl](2+) (2) (bpy=2,2'-bipyridyl, phen=1,10-phenanthroline), have been synthesized and characterized. The critical micelle concentration (CMC) values of these complexes in aqueous solution were obtained from conductance measurements. The specific conductivity data (at 298, 308, 318 and 328 K) served for the evaluation of the temperature-dependent CMC and the thermodynamics of micellization (DeltaG(m)(0),DeltaH(m)(0)and DeltaS(m)(0)). The interaction between these complexes and calf thymus DNA in aqueous solution was investigated adopting electronic absorption spectroscopy, emission spectroscopy and viscosity measurements. Results suggest that the two complexes can bind to DNA via groove binding, van der Waals interactions and/or electrostatic interactions. The complexes showed moderate antibacterial and antifungal activities against certain selected microorganisms. The cytotoxic activity of the complexes on HBL-100 human breast cancer cells was determined adopting MTT assay and specific staining techniques, which revealed that the viability of the cells thus treated was significantly decreased and the cells succumbed to apoptosis as seen in the changes in the nuclear morphology and cytoplasmic features. Furthermore, the influence of complexes on normal cell lines from green monkey kidney was also determined and the results indicate that the effect is small on inhibition of viability.
Asunto(s)
Antibacterianos/química , Antifúngicos/química , Antineoplásicos/química , Compuestos Organometálicos/química , Compuestos Organometálicos/farmacología , Animales , Antibacterianos/síntesis química , Antibacterianos/farmacología , Antifúngicos/síntesis química , Antifúngicos/farmacología , Antineoplásicos/síntesis química , Antineoplásicos/farmacología , Bacterias/efectos de los fármacos , Línea Celular , Línea Celular Tumoral , Cobalto/química , ADN/química , Diseño de Fármacos , Etidio/química , Hongos/efectos de los fármacos , Humanos , Potencial de la Membrana Mitocondrial/efectos de los fármacos , Micelas , Compuestos Organometálicos/metabolismoRESUMEN
A new class of surfactant-cobalt(III) complex ions of the type, cis-[Co(X)(2)(C(14)H(29)NH(2))Cl](2+) (where X=ethylenediamine (en), or 2,2'-bipyridyl (bpy), or 1,10-phenanthroline (phen)) and cis-[Co(trien)(C(14)H(29)NH(2))Cl](2+) (trien=triethylenetetramine) were synthesized and characterized by IR, NMR, UV-visible electronic absorption spectra, elemental analysis and metal analysis. The critical micelle concentration (CMC) values of these surfactant-cobalt(III) complexes in aqueous solution were obtained from conductance measurements. Specific conductivity data (at 298, 308, 318 and 328 K) served for the evaluation of the temperature-dependent CMC and the thermodynamics of micellization (DeltaG(0)(m), DeltaH(0)(m) and DeltaS(0)(m)). Interactions between calf thymus DNA and the surfactant-cobalt(III) complexes in aqueous solution have been investigated by electronic absorption spectroscopy, emission spectroscopy and viscosity measurements. The electrostatic interactions, van der Waals interactions and/or partial intercalative binding have been observed in these systems. The surfactant-cobalt(III) complexes were screened for their antibacterial and antifungal activities against various microorganisms. The results were compared with the standard drugs, Ciprofloxacin and Fluconazole respectively.