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1.
Sci Rep ; 13(1): 20889, 2023 11 28.
Artículo en Inglés | MEDLINE | ID: mdl-38017141

RESUMEN

Invasive wild pigs (Sus scrofa) are one of the most widespread, destructive vertebrate species globally. Their success can largely be attributed to their generalist diets, which are dominated by plant material but also include diverse animal taxa. Wild pigs are demonstrated nest predators of ground-nesting birds and reptiles, and likely pose a threat to amphibians given their extensive overlap in wetland use. DNA metabarcoding of fecal samples from 222 adult wild pigs culled monthly from 2017 to 2018 revealed a diverse diet dominated by plant material, with 166 plant genera from 56 families and 18 vertebrate species identified. Diet composition varied seasonally with availability for plants and was consistent between sexes. Amphibians were the most frequent vertebrate group consumed and represented the majority of vertebrate species detected, suggesting amphibians are potentially vulnerable to predation by wild pigs in our study region. Mammal, reptile, and bird species were also detected in pig diets, but infrequently. Our results highlight the need for research on the impacts of wild pigs on amphibians to better inform management and conservation of imperiled species.


Asunto(s)
Código de Barras del ADN Taxonómico , ADN , Humanos , Animales , Porcinos , Anfibios/genética , Aves , Sudeste de Estados Unidos , Reptiles , Plantas , Sus scrofa/genética
2.
Ecol Evol ; 13(5): e10136, 2023 May.
Artículo en Inglés | MEDLINE | ID: mdl-37250446

RESUMEN

Skewed sex ratios at birth are widely reported in wild populations, however, the extent to which parents are able to modulate the sex ratio of offspring to maximize their own fitness remains unclear. This is particularly true for highly polytocous species as maximizing fitness may include trade-offs between sex ratio and the size and number of offspring in litters. In such cases, it may be adaptive for mothers to adjust both the number of offspring per litter and offspring sex to maximize individual fitness. Investigating maternal sex allocation in wild pigs (Sus scrofa) under stochastic environmental conditions, we predicted that under favorable conditions, high-quality mothers (larger and older) would produce male-biased litters and invest more in producing larger litters with more males. We also predicted sex ratio would vary relative to litter size, with a male-bias among smaller litters. We found evidence that increasing wild boar ancestry, maternal age and condition, and resource availability may weakly contribute to male-biased sex ratio, however, unknown factors not measured in this study are assumed to be more influential. High-quality mothers allocated more resources to litter production, but this relationship was driven by adjustment of litter size, not sex ratio. There was no relationship between sex ratio and litter size. Collectively, our results emphasized that adjustment of litter size appeared to be the primary reproductive characteristic manipulated in wild pigs to increase fitness rather than adjustment of offspring sex ratio.

3.
Pest Manag Sci ; 79(10): 3819-3829, 2023 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-37218996

RESUMEN

BACKGROUND: Data on the movement behavior of translocated wild pigs is needed to develop appropriate response strategies for containing and eliminating new source populations following translocation events. We conducted experimental trials to compare the home range establishment and space-use metrics, including the number of days and distance traveled before becoming range residents, for wild pigs translocated with their social group and individually. RESULTS: We found wild pigs translocated with their social group made less extensive movements away from the release location and established a stable home range ~5 days faster than those translocated individually. We also examined how habitat quality impacted the home range sizes of translocated wild pigs and found wild pigs maintained larger ranges in areas with higher proportion of low-quality habitat. CONCLUSION: Collectively, our findings suggest translocations of invasive wild pigs have a greater probability of establishing a viable population near the release site when habitat quality is high and when released with members of their social unit compared to individuals moved independent of their social group or to low-quality habitat. However, all wild pigs translocated in our study made extensive movements from their release location, highlighting the potential for single translocation events of either individuals or groups to have far-reaching consequences within a much broader landscape beyond the location where they are released. These results highlight the challenges associated with containing populations in areas where illegal introduction of wild pigs occurs, and the need for rapid response once releases are identified. © 2023 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.


Asunto(s)
Ecosistema , Sus scrofa , Animales , Porcinos , Sus scrofa/fisiología , Fenómenos de Retorno al Lugar Habitual , Movimiento , Estructura Social
4.
Environ Pollut ; 306: 119359, 2022 Aug 01.
Artículo en Inglés | MEDLINE | ID: mdl-35487469

RESUMEN

Genetic effects and radioactive contamination of large mammals, including wild boar (Sus scrofa), have been studied in Japan because of dispersal of radionuclides from the Fukushima Dai-ichi Nuclear Power Plant in 2011. Such studies have generally demonstrated a declining trend in measured radiocesium body burdens in wildlife. Estimating radiation exposure to wildlife is important to understand possible long-term impacts. Here, radiation exposure was evaluated in 307 wild boar inhabiting radioactively contaminated areas (50-8000 kBq m-2) in Fukushima Prefecture from 2016 to 2019, and genetic markers were examined to assess possible germline mutations caused by chronic radiation exposures to several generations of wild boar. Internal Cs activity concentrations in boar remained high in areas near the power plant with the highest concentration of 54 kBq kg-1 measured in 2019. Total dose rates to wild boar ranged from 0.02 to 36 µGy h-1, which was primarily attributed to external radiation exposure, and dose rates to the maximally exposed animals were above the generic no-effects benchmark of 10 µGy h-1. Using the estimated age of each animal, lifetime radiation doses ranged from <0.1 mGy to 700 mGy. Despite chronic exposures, the genetic analyses showed no significant accumulation of mutation events. Because wild boar is an occasional human dietary item in Japan, effective dose to humans from ingesting contaminated wild boar meat was calculated. Hypothetical consumption of contaminated wild boar meat from radioactively contaminated areas in Fukushima, at the per capita pork consumption rate (12.9 kg y-1), would result in an average effective annual dose of 0.9 mSv y-1, which is below the annual ingestion limit of 1 mSv y-1. Additionally, a consumption rate of about 1.4 kg y-1 of the most contaminated meat in this study would not exceed annual ingestion limits.


Asunto(s)
Accidente Nuclear de Fukushima , Monitoreo de Radiación , Animales , Animales Salvajes , Radioisótopos de Cesio/análisis , Mutación de Línea Germinal , Humanos , Japón , Carne/análisis , Dosis de Radiación , Sus scrofa/genética , Porcinos
5.
Environ Int ; 155: 106675, 2021 10.
Artículo en Inglés | MEDLINE | ID: mdl-34120002

RESUMEN

The health effects associated with chronic low-dose, low-dose rate (LD-LDR) exposures to environmental radiation are uncertain. All dose-effect studies conducted outside controlled laboratory conditions are challenged by inherent complexities of ecological systems and difficulties quantifying dose to free-ranging organisms in natural environments. Consequently, the effects of chronic LD-LDR radiation exposures on wildlife health remain poorly understood and much debated. Here, samples from wild boar (Sus scrofa leucomystax) and rat snakes (Elaphe spp.) were collected between 2016 and 2018 across a gradient of radiation exposures in Fukushima, Japan. In vivo biomarkers of DNA damage and stress were evaluated as a function of multiple measurements of radiation dose. Specifically, we assessed frequencies of dicentric chromosomes (Telomere-Centromere Fluorescence in situ Hybridization: TC-FISH), telomere length (Telo-FISH, qPCR), and cortisol hormone levels (Enzyme Immunoassay: EIA) in wild boar, and telomere length (qPCR) in snakes. These biological parameters were then correlated to robust calculations of radiation dose rate at the time of capture and plausible upper bound lifetime dose, both of which incorporated internal and external dose. No significant relationships were observed between dicentric chromosome frequencies or telomere length and dose rate at capture or lifetime dose (p value range: 0.20-0.97). Radiation exposure significantly associated only with cortisol, where lower concentrations were associated with higher dose rates (r2 = 0.58; p < 0.0001), a relationship that was likely due to other (unmeasured) factors. Our results suggest that wild boar and snakes chronically exposed to LD-LDR radiation sufficient to prohibit human occupancy were not experiencing significant adverse health effects as assessed by biomarkers of DNA damage and stress.


Asunto(s)
Accidente Nuclear de Fukushima , Monitoreo de Radiación , Animales , Animales Salvajes , Radioisótopos de Cesio/análisis , Daño del ADN , Humanos , Hibridación Fluorescente in Situ , Japón , Plantas de Energía Nuclear
6.
Sci Rep ; 11(1): 11033, 2021 05 26.
Artículo en Inglés | MEDLINE | ID: mdl-34040083

RESUMEN

Understanding factors influencing survival of neonates for wild species is important for successful management, particularly for determining drivers of population dynamics. Wild pigs (Sus scrofa) are invasive and populations are rapidly increasing in part due to high reproductive capacity. Survival of adults is generally high, however, survival of piglets, and particularly neonates, is largely unknown. We located neonates at the natal nest and quantified survival in relation to individual and maternal biological attributes, and environmental variables. During 2017-2020, we captured 50 neonates from 13 litters and documented 28 mortalities (56%) over six weeks. Survival was positively influenced by pelage coloration, likely as a form of camouflage from predators. Male neonates had higher survival. They were born larger than females, which could be beneficial for thermoregulation and competition for milk. Neonates born to larger sows had lower survival. Sow size was positively correlated with litter size, and this finding may reflect the increased nutritional demands of sustaining large litters, or difficulties in defending more neonates against predators. Neonates born in warmer months had higher survival than those born in cooler months. Neonates are inefficient thermoregulators, thus being born in warmer months could be beneficial for maintaining homeostasis as well as access to more food resources. These are the largest and most complete data for neonate wild pig survival and will inform population models for the development of management strategies to reduce negative impacts of this destructive invasive species on native ecosystems.


Asunto(s)
Mamíferos , Animales , Ecosistema , Femenino , Lactancia , Tamaño de la Camada , Parto , Embarazo , Reproducción , Destete
7.
J Anim Ecol ; 90(4): 820-833, 2021 04.
Artículo en Inglés | MEDLINE | ID: mdl-33340089

RESUMEN

Contact heterogeneity among hosts determines invasion and spreading dynamics of infectious disease, thus its characterization is essential for identifying effective disease control strategies. Yet, little is known about the factors shaping contact networks in many wildlife species and how wildlife management actions might affect contact networks. Wild pigs in North America are an invasive, socially structured species that pose a health concern for domestic swine given their ability to transmit numerous devastating diseases such as African swine fever (ASF). Using proximity loggers and GPS data from 48 wild pigs in Florida and South Carolina, USA, we employed a probabilistic framework to estimate weighted contact networks. We determined the effects of sex, social group and spatial distribution (monthly home-range overlap and distance) on wild pig contact. We also estimated the impacts of management-induced perturbations on contact and inferred their effects on ASF establishment in wild pigs with simulation. Social group membership was the primary factor influencing contacts. Between-group contacts depended primarily on space use characteristics, with fewer contacts among groups separated by >2 km and no contacts among groups >4 km apart within a month. Modelling ASF dynamics on the contact network demonstrated that indirect contacts resulting from baiting (a typical method of attracting wild pigs or game species to a site to enhance recreational hunting) increased the risk of disease establishment by ~33% relative to direct contact. Low-intensity population reduction (<5.9% of the population) had no detectable impact on contact structure but reduced predicted ASF establishment risk relative to no population reduction. We demonstrate an approach for understanding the relative role of spatial, social and individual-level characteristics in shaping contact networks and predicting their effects on disease establishment risk, thus providing insight for optimizing disease control in spatially and socially structured wildlife species.


Asunto(s)
Virus de la Fiebre Porcina Africana , Fiebre Porcina Africana , Enfermedades de los Porcinos , Animales , Florida , América del Norte , South Carolina , Sus scrofa , Porcinos , Enfermedades de los Porcinos/epidemiología
8.
Ecol Appl ; 30(1): e02015, 2020 01.
Artículo en Inglés | MEDLINE | ID: mdl-31596984

RESUMEN

Functional responses describe how changing resource availability affects consumer resource use, thus providing a mechanistic approach to prediction of the invasibility and potential damage of invasive alien species (IAS). However, functional responses can be context dependent, varying with resource characteristics and availability, consumer attributes, and environmental variables. Identifying context dependencies can allow invasion and damage risk to be predicted across different ecoregions. Understanding how ecological factors shape the functional response in agro-ecosystems can improve predictions of hotspots of highest impact and inform strategies to mitigate damage across locations with varying crop types and availability. We linked heterogeneous movement data across different agro-ecosystems to predict ecologically driven variability in the functional responses. We applied our approach to wild pigs (Sus scrofa), one of the most successful and detrimental IAS worldwide where agricultural resource depredation is an important driver of spread and establishment. We used continental-scale movement data within agro-ecosystems to quantify the functional response of agricultural resources relative to availability of crops and natural forage. We hypothesized that wild pigs would selectively use crops more often when natural forage resources were low. We also examined how individual attributes such as sex, crop type, and resource stimulus such as distance to crops altered the magnitude of the functional response. There was a strong agricultural functional response where crop use was an accelerating function of crop availability at low density (Type III) and was highly context dependent. As hypothesized, there was a reduced response of crop use with increasing crop availability when non-agricultural resources were more available, emphasizing that crop damage levels are likely to be highly heterogeneous depending on surrounding natural resources and temporal availability of crops. We found significant effects of crop type and sex, with males spending 20% more time and visiting crops 58% more often than females, and both sexes showing different functional responses depending on crop type. Our application demonstrates how commonly collected animal movement data can be used to understand context dependencies in resource use to improve our understanding of pest foraging behavior, with implications for prioritizing spatiotemporal hotspots of potential economic loss in agro-ecosystems.


Asunto(s)
Productos Agrícolas , Ecosistema , Agricultura , Animales , Femenino , Masculino , Movimiento
9.
Ecol Evol ; 8(16): 8433-8447, 2018 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-30250713

RESUMEN

Lactation is the most energetically demanding stage of reproduction in female mammals. Increased energetic allocation toward current reproduction may result in fitness costs, although the mechanisms underlying these trade-offs are not well understood. Trade-offs during lactation may include reduced energetic allocation to cellular maintenance, immune response, and survival and may be influenced by resource limitation. As the smallest marine mammal, sea otters (Enhydra lutris) have the highest mass-specific metabolic rate necessitating substantial energetic requirements for survival. To provide the increased energy needed for lactation, female sea otters significantly increase foraging effort, especially during late-lactation. Caloric insufficiency during lactation is reflected in the high numbers of maternal deaths due to End-Lactation Syndrome in the California subpopulation. We investigated the effects of lactation and resource limitation on maternal stress responses, metabolic regulation, immune function, and antioxidant capacity in two subspecies of wild sea otters (northern: E. l. nereis and southern: E. l. kenyoni) within the California, Washington, and Alaska subpopulations. Lactation and resource limitation were associated with reduced glucocorticoid responses to acute capture stress. Corticosterone release was lower in lactating otters. Cortisol release was lower under resource limitation and suppression during lactation was only evident under resource limitation. Lactation and resource limitation were associated with alterations in thyroid hormones. Immune responses and total antioxidant capacity were not reduced by lactation or resource limitation. Southern sea otters exhibited higher concentrations of antioxidants, immunoglobulins, and thyroid hormones than northern sea otters. These data provide evidence for allocation trade-offs during reproduction and in response to nutrient limitation but suggest self-maintenance of immune function and antioxidant defenses despite energetic constraints. Income-breeding strategists may be especially vulnerable to the consequences of stress and modulation of thyroid function when food resources are insufficient to support successful reproduction and may come at a cost to survival, and thereby influence population trends.

10.
Gen Comp Endocrinol ; 253: 70-78, 2017 11 01.
Artículo en Inglés | MEDLINE | ID: mdl-28888695

RESUMEN

The critically endangered Radiated Tortoise (Astrochelys radiata) is endemic to the southern coastlines of Madagascar. Once common, wild populations of this tortoise have undergone dramatic declines in recent years. Although there have been studies documenting reproductive activities, reproductive physiological parameters are unknown yet may be crucial in the recovery of the species. Over four research seasons in remote field locations native to A. radiata, we surveyed for, radio-tracked, and sampled wild, free ranging tortoises. We sampled and measured stress and reproductive parameters (corticosterone [CORT], testosterone [T], estradiol-17ß [E2], and progesterone [P]) in 311 plasma samples from 203 wild A. radiata, capturing their active period. Generally, hormone concentrations were associated with body condition, temperature, and humidity. There was wide variation in CORT that varied monthly and by group. Juvenile tortoises maintained more than twice the mean basal CORT concentrations than either adult sex, with the most dramatic distinctions in the middle of the wet season. For adult sex hormones, the last months of the dry season and into the wet season when ground humidities are low and just begin to rise prior to temperature declines, male T concentrations gradually increased to a peak before returning to near undetectable values into the dry season. We had limited data for T concentrations in females, but found average T concentrations were much lower than in males and positively correlated with larger female home range sizes. For female hormone cycles, E2 also peaked in the early 1/3 of the wet season along with male T, and was followed by an uptick in P which correlates to the putative ovulatory cycle. Females tracked over four years showed variation in patterns of P, indicating that number and frequency of clutches vary. Our results suggest that 1) there is high species plasticity in response to stress; 2) A. radiata reproductive cycling is somewhat dissociated with courtship timing and is instead triggered by environmental cues; and 3) individual female reproductive output is irregular. This study is oone of the first to document and describe multi-year seasonal stress and reproductive hormones in a free-ranging Malagasy chelonian. These data may be used to identify key high-production habitats for conservation, and aide in captive management and reproduction in assurance colonies for species health and survival.


Asunto(s)
Animales Salvajes/sangre , Animales Salvajes/fisiología , Hormonas Esteroides Gonadales/sangre , Reproducción/fisiología , Estaciones del Año , Estrés Fisiológico , Tortugas/sangre , Tortugas/fisiología , Animales , Corticosterona/sangre , Ambiente , Estradiol/sangre , Femenino , Madagascar , Masculino , Progesterona/sangre , Reproducibilidad de los Resultados , Testosterona/sangre
11.
J Wildl Dis ; 52(2): 307-18, 2016 04 28.
Artículo en Inglés | MEDLINE | ID: mdl-26967137

RESUMEN

Sea otters ( Enhydra lutris ) have exceptionally high energetic requirements, which nearly double during lactation and pup care. Thus, females are extremely vulnerable to caloric insufficiency. Despite a number of compensatory strategies, the metabolic challenge of reproduction culminates in numerous maternal deaths annually. Massive depletion of energy reserves results in a case presentation that we define as end-lactation syndrome (ELS), characterized by moderate to severe emaciation not attributable to a concurrent, independent disease process in females dying during late pup care or postweaning. We compiled detailed data for 108 adult female southern sea otters ( Enhydra lutris nereis) examined postmortem that stranded in California, US, 2005-12, and assessed pathology, reproductive status, and the location and timing of stranding. We introduce simple, grossly apparent, standardized physical criteria to assess reproductive stage for female sea otters. We also describe ELS, examine associated risk factors, and highlight female life history strategies that likely optimize reproduction and survival. Our data suggest that females can reset both the timing and energetic demands of reproduction through fetal loss, pup abandonment, or early weaning as part of specific physiologic checkpoints during each reproductive cycle. Females appear to preload nutritionally during delayed implantation and gestation to increase fitness and reproductive success. We found that ELS was a major cause of death, affecting 56% of enrolled adult females. Peak ELS prevalence occurred in late spring, possibly reflecting the population trend toward fall/winter pupping. Increasing age and number of pregnancies were associated with a higher risk of ELS. Although the proportion of ELS females was highest in areas with dense sea otter populations, cases were recovered throughout the range, suggesting that death from ELS is associated with, but not solely caused by, population resource limitation.


Asunto(s)
Metabolismo Energético/fisiología , Lactancia/fisiología , Nutrias , Animales , California , Emaciación , Femenino , Nutrias/fisiología , Reproducción/fisiología , Estaciones del Año
12.
J Chromatogr A ; 1401: 1-8, 2015 Jul 03.
Artículo en Inglés | MEDLINE | ID: mdl-26008594

RESUMEN

We have developed a solid phase microextraction (SPME) sampling method using fused silica lined bottles (400 ml) to collect, store, and stabilize a headspace subsample from the source for subsequent offline, repetitive analyses of the gas using fiber-based SPME. The method enables long-term stability for repeated offline analysis of the organic species collected from the source headspace and retains all the advantages of fiber SPME sampling (e.g. rapid extraction, solvent free, simple and inexpensive) while providing additional advantages. Typically, the analytes collected on the SPME fiber must be desorbed and analyzed immediately to mitigate analyte loss or contamination. The new SPME sampling method, conducted offline using carboxen/polydimethylsiloxane (carboxen/PDMS - 85 µm) coated fibers, has been shown to be identical to in situ SPME sampling of a headspace acquired from an 80 component organic matrix with reproducibility demonstrated to be less than %RSD=7.0% for replicate samples measured over a 30-day period. In addition, repetitive samplings from one headspace aliquot are possible using one or more fibers and fiber types as well as quantitative options such as internal standard addition as demonstrated in a feasibility study using a benzene/toluene/xylene (BTX; 1 ppmv) certified gas standard, in which the SPME measurement precision (%RSD) was improved by a factor of 1.5-1.9 compared to the use of an external standard.


Asunto(s)
Técnicas de Química Analítica/métodos , Gases/química , Dióxido de Silicio/química , Microextracción en Fase Sólida/instrumentación , Benceno/análisis , Técnicas de Química Analítica/instrumentación , Reproducibilidad de los Resultados , Tolueno/análisis , Xilenos/análisis
13.
Anal Chem ; 84(23): 10478-84, 2012 Dec 04.
Artículo en Inglés | MEDLINE | ID: mdl-23126561

RESUMEN

Organophosphorus compounds represent a large class of molecules that include pesticides, flame-retardants, biologically relevant molecules, and chemical weapons agents (CWAs). The detection and identification of organophosphorus molecules, particularly in the cases of pesticides and CWAs, are paramount to the verification of international treaties by various organizations. To that end, novel analytical methodologies that can provide additional support to traditional analyses are important for unambiguous identification of these compounds. We have developed an NMR method that selectively edits for organophosphorus compounds via (31)P-(1)H heteronuclear single quantum correlation (HSQC) and provides an additional chromatographic-like separation based on self-diffusivities of the individual species via (1)H diffusion-ordered spectroscopy (DOSY): (1)H-(31)P HSQC-DOSY. The technique is first validated using the CWA VX (O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate) by traditional two-dimensional DOSY spectra. We then extend this technique to a complex mixture of VX degradation products and identify all the main phosphorus-containing byproducts generated after exposure to a zinc-cyclen organometallic homogeneous catalyst.

14.
Phys Chem Chem Phys ; 14(10): 3316-22, 2012 Mar 14.
Artículo en Inglés | MEDLINE | ID: mdl-22298156

RESUMEN

Computational studies of condensed-phase chemical reactions are challenging in part because of complexities in understanding the effects of the solvent environment on the reacting chemical species. Such studies are further complicated due to the demanding computational resources required to implement high-level ab initio quantum chemical methods when considering the solvent explicitly. Here, we use first-principles molecular dynamics simulations to examine condensed-phase decontamination reactions of V-type nerve agents in an explicit aqueous solvent. Our results include a detailed study of hydrolysis, base-hydrolysis, and nucleophilic oxidation of both VX and R-VX, as well as their protonated counterparts (i.e., VXH(+) and R-VXH(+)). The decontamination mechanisms and chemical reaction energy barriers, as determined from our simulations, are found to be in good agreement with experiment. The results demonstrate the applicability of using such simulations to assist in understanding new decontamination technologies or other applications that require computational screening of condensed-phase chemical reaction mechanisms.


Asunto(s)
Sustancias para la Guerra Química/química , Simulación de Dinámica Molecular , Compuestos Organotiofosforados/química , Hidrólisis , Modelos Moleculares , Estructura Molecular , Oxidación-Reducción , Solventes/química , Agua/química
15.
J Phys Chem B ; 114(30): 9729-36, 2010 Aug 05.
Artículo en Inglés | MEDLINE | ID: mdl-20617846

RESUMEN

Radiation-induced degradation of polymeric materials occurs through numerous, simultaneous, competing chemical reactions. Although degradation is typically found to be linear in adsorbed dose, some silicone materials exhibit nonlinear dose dependence due to dose-dependent dominant degradation pathways. We have characterized the effects of radiative and thermal degradation on a model filled-PDMS system, Sylgard 184 (commonly used in electronic encapsulation and in biomedical applications), using traditional mechanical testing, NMR spectroscopy, and sample headspace analysis using solid-phase microextraction (SPME) followed by gas chromatography/mass spectrometry (GC/MS). The mechanical data and (1)H spin-echo NMR spectra indicated that radiation exposure leads to predominantly cross-linking over the cumulative dose range studied (0-250 kGy) with a rate roughly linear with dose. (1)H multiple-quantum NMR spectroscopy detected a bimodal distribution in the network structure, as expected from the proposed structure of Sylgard 184. The MQ NMR spectra further indicated that the radiation-induced structural changes were not linear in adsorbed dose and that competing chain scission mechanisms made a greater contribution to the overall degradation process in the range of 50-100 kGy (although cross-linking still dominated). The SPME-GC/MS data were analyzed using principal component analysis (PCA), which identified subtle changes in the distributions of degradation products (the cyclic siloxanes and other components of the material) as a function of age that provide insight into the dominant degradation pathways at low and high adsorbed dose.

16.
J Phys Chem B ; 111(45): 12977-84, 2007 Nov 15.
Artículo en Inglés | MEDLINE | ID: mdl-17958412

RESUMEN

Thermal degradation of a filled, cross-linked siloxane material synthesized from poly(dimethylsiloxane) chains of three different average molecular weights and with two different cross-linking species has been studied by (1)H multiple quantum (MQ) NMR methods. Multiple domains of polymer chains were detected by MQ NMR exhibiting residual dipolar coupling () values of 200 and 600 Hz, corresponding to chains with high average molecular weight between cross-links and chains with low average molecular weight between cross-links or near the multifunctional cross-linking sites. Characterization of the values and changes in distributions present in the material were studied as a function of time at 250 degrees C and indicate significant time-dependent degradation. For the domains with low , a broadening in the distribution was observed with aging time. For the domain with high , increases in both the mean and the width in were observed with increasing aging time. Isothermal thermal gravimetric analysis reveals a 3% decrease in weight over 20 h of aging at 250 degrees C. Degraded samples also were analyzed by traditional solid-state (1)H NMR techniques, and off-gassing products were identified by solid-phase microextraction followed by gas chromatography-mass spectrometry. The results, which will be discussed here, suggest that thermal degradation proceeds by complex competition between oxidative chain scissioning and postcuring cross-linking that both contribute to embrittlement.

17.
J Magn Reson ; 189(1): 121-9, 2007 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-17897853

RESUMEN

Nuclear Magnetic Resonance (NMR) is unsurpassed in its ability to non-destructively probe chemical identity. Portable, low-cost NMR sensors would enable on-site identification of potentially hazardous substances, as well as the study of samples in a variety of industrial applications. Recent developments in RF microcoil construction (i.e. coils much smaller than the standard 5mm NMR RF coils), have dramatically increased NMR sensitivity and decreased the limits-of-detection (LOD). We are using advances in laser pantographic microfabrication techniques, unique to LLNL, to produce RF microcoils for field deployable, high sensitivity NMR-based detectors. This same fabrication technique can be used to produce imaging coils for MRI as well as for standard hardware shimming or "ex-situ" shimming of field inhomogeneities typically associated with inexpensive magnets. This paper describes a portable NMR system based on the use of a 2 kg hand-held permanent magnet, laser-fabricated microcoils, and a compact spectrometer. The main limitations for such a system are the low resolution and sensitivity associated with the low field values and quality of small permanent magnets, as well as the lack of large amounts of sample of interest in most cases. The focus of the paper is on the setting up of this system, initial results, sensitivity measurements, discussion of the limitations and future plans. The results, even though preliminary, are promising and provide the foundation for developing a portable, inexpensive NMR system for chemical analysis. Such a system will be ideal for chemical identification of trace substances on site.


Asunto(s)
Espectroscopía de Resonancia Magnética/instrumentación , Algoritmos , Diseño de Equipo , Espectroscopía de Resonancia Magnética/economía , Espectroscopía de Resonancia Magnética/métodos
18.
J Chem Phys ; 123(10): 104311, 2005 Sep 08.
Artículo en Inglés | MEDLINE | ID: mdl-16178601

RESUMEN

The energy-transfer dynamics of high-pressure molecular H(2) gas initially prepared in the |X (1)Sigma(g) (+),v = 1,J = 1 state using stimulated Raman pumping are probed with rotational Raman scattering. A computer simulation that incorporates the effects of collision-induced vibrational energy transfer is described and used to fit the experimental Raman scattering results obtained as a function of the pump/probe delay time. The 4.78 x 10(-14) +/- 3.85 x 10(-16) cm(3) s(-1) molecule(-1) vibrational energy-transfer rate for decay from the |X (1)Sigma(g) (+),v = 1,J = 1 >state compares well with other lower-pressure studies.


Asunto(s)
Simulación por Computador , Transferencia de Energía , Hidrógeno/química , Modelos Teóricos , Termodinámica
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