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1.
J Neural Eng ; 20(1)2023 01 18.
Artículo en Inglés | MEDLINE | ID: mdl-36535037

RESUMEN

Objective.Although electrical vagus nerve stimulation has been shown to augment parasympathetic control of the heart, the effects of electrical conduction block have been less rigorously characterized. Previous experiments have demonstrated that direct current (DC) nerve block can be applied safely and effectively in the autonomic system, but additional information about the system dynamics need to be characterized to successfully deploy DC nerve block to clinical practice.Approach.The dynamics of the heart rate (HR) from DC nerve block of the vagus nerve were measured by stimulating the vagus nerve to lower the HR, and then applying DC block to restore normal rate. DC block achieved rapid, complete block, as well as partial block at lower amplitudes.Main Results. Complete block was also achieved using lower amplitudes, but with a slower induction time. The time for DC to induce complete block was significantly predicted by the amplitude; specifically, the amplitude expressed as a percentage of the current required for a rapid, 60 s induction time. Recovery times after the cessation of DC block could occur both instantly, and after a significant delay. Both blocking duration and injected charge were significant in predicting the delay in recovery to normal conduction.Significance. While these data show that broad features such as induction and recovery can be described well by the DC parameters, more precise features of the HR, such as the exact path of the induction and recoveries, are still undefined. These findings show promise for control of the cardiac autonomic nervous system, with potential to expand to the sympathetic inputs as well.


Asunto(s)
Estimulación del Nervio Vago , Nervio Vago , Ratas , Animales , Frecuencia Cardíaca/fisiología , Nervio Vago/fisiología , Corazón/inervación , Corazón/fisiología , Estimulación del Nervio Vago/métodos
2.
Glob Chang Biol ; 29(3): 648-667, 2023 02.
Artículo en Inglés | MEDLINE | ID: mdl-36278894

RESUMEN

Anthropogenic climate change is resulting in spatial redistributions of many species. We assessed the potential effects of climate change on an abundant and widely distributed group of diving birds, Eudyptes penguins, which are the main avian consumers in the Southern Ocean in terms of biomass consumption. Despite their abundance, several of these species have undergone population declines over the past century, potentially due to changing oceanography and prey availability over the important winter months. We used light-based geolocation tracking data for 485 individuals deployed between 2006 and 2020 across 10 of the major breeding locations for five taxa of Eudyptes penguins. We used boosted regression tree modelling to quantify post-moult habitat preference for southern rockhopper (E. chrysocome), eastern rockhopper (E. filholi), northern rockhopper (E. moseleyi) and macaroni/royal (E. chrysolophus and E. schlegeli) penguins. We then modelled their redistribution under two climate change scenarios, representative concentration pathways RCP4.5 and RCP8.5 (for the end of the century, 2071-2100). As climate forcings differ regionally, we quantified redistribution in the Atlantic, Central Indian, East Indian, West Pacific and East Pacific regions. We found sea surface temperature and sea surface height to be the most important predictors of current habitat for these penguins; physical features that are changing rapidly in the Southern Ocean. Our results indicated that the less severe RCP4.5 would lead to less habitat loss than the more severe RCP8.5. The five taxa of penguin may experience a general poleward redistribution of their preferred habitat, but with contrasting effects in the (i) change in total area of preferred habitat under climate change (ii) according to geographic region and (iii) the species (macaroni/royal vs. rockhopper populations). Our results provide further understanding on the regional impacts and vulnerability of species to climate change.


Asunto(s)
Spheniscidae , Humanos , Animales , Fitomejoramiento , Ecosistema , Predicción , Cambio Climático , Océanos y Mares
3.
Bioelectron Med ; 8(1): 11, 2022 Jul 27.
Artículo en Inglés | MEDLINE | ID: mdl-35883133

RESUMEN

OBJECTIVES: KiloHertz frequency alternating current waveforms produce conduction block in peripheral nerves. It is not clearly known how the waveform shape affects block outcomes, and if waveform effects are frequency dependent. We determined the effects of waveform shape using two types of electrodes. MATERIALS AND METHODS: Acute in-vivo experiments were performed on 12 rats. Bipolar electrodes were used to electrically block motor nerve impulses in the sciatic nerve, as measured using force output from the gastrocnemius muscle. Three blocking waveforms were delivered (sinusoidal, square and triangular) at 6 frequencies (10-60 kHz). Bare platinum electrodes were compared with carbon black coated electrodes. We determined the minimum amplitude that could completely block motor nerve conduction (block threshold), and measured properties of the onset response, which is a transient period of nerve activation at the start of block. In-vivo results were compared with computational modeling conducted using the NEURON simulation environment using a nerve membrane model modified for stimulation in the kilohertz frequency range. RESULTS: For the majority of parameters, in-vivo testing and simulations showed similar results: Block thresholds increased linearly with frequency for all three waveforms. Block thresholds were significantly different between waveforms; lowest for the square waveform and highest for triangular waveform. When converted to charge per cycle, square waveforms required the maximum charge per phase, and triangular waveforms the least. Onset parameters were affected by blocking frequency but not by waveform shape. Electrode comparisons were performed only in-vivo. Electrodes with carbon black coatings gave significantly lower block thresholds and reduced onset responses across all blocking frequencies. For 10 and 20 kHz, carbon black coating significantly reduced the charge required for nerve block. CONCLUSIONS: We conclude that both sinusoidal and square waveforms at frequencies of 20 kHz or higher would be optimal. Future investigation of carbon black or other high charge capacity electrodes may be useful in achieving block with lower BTs and onsets. These findings will be of importance for designing clinical nerve block systems.

4.
Front Nutr ; 9: 1060212, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-36742002

RESUMEN

Intestinal microbiota, diet, and physical activity are inextricably linked to inflammation occurring in the presence of tumor progression and declining neurocognition. This study aimed to explore how fecal microbiota, inflammatory biomarkers, and neurocognitive behavior are influenced by voluntary exercise and surplus dietary protein and folic acid which are common health choices. Dietary treatments provided over 8 weeks to C57BL/CJ male mice (N = 76) were: Folic Acid (FA) Protein (P) Control (FPC, 17.9% P; 2 mgFA/kg); Folic Acid Deficient (FAD); Folic Acid Supplemented (FAS; 8 mgFA/kg); Low Protein Diet (LPD, 6% P); and High Protein Diet (HPD, 48% P). FAS mice had decreased plasma HCys (p < 0.05), therefore confirming consumption of FA. Objectives included examining influence of exercise using Voluntary Wheel Running (VWR) upon fecal microbiota, inflammatory biomarkers C - reactive protein (CRP), Vascular Endothelial Growth Factor (VEGF), Interleukin-6 (IL-6), nuclear factor kappa ß subunit (NF-κßp65), Caspase-3 (CASP3), Tumor Necrosis Factor-alpha (TNF-α), and neurocognitive behavior. CRP remained stable, while a significant exercise and dietary effect was notable with decreased VEGF (p < 0.05) and increased CASP3 (p < 0.05) for exercised HPD mice. Consumption of FAS did significantly increase (p < 0.05) muscle TNF-α and the ability to build a nest (p < 0.05) was significantly decreased for both FAD and LPD exercised mice. Rearing behavior was significantly increased (p < 0.05) in mice fed HPD. An emerging pattern with increased dietary protein intake revealed more distance explored in Open Field Testing. At week 1, both weighted and unweighted UniFrac principal coordinates analysis yielded significant clustering (permanova, p ≤ 0.05) associated with the specific diets. Consumption of a HPD diet resulted in the most distinct fecal microbiota composition. At the phylum level-comparing week 1 to week 8-we report a general increase in the Firmicutes/Bacteroidetes ratio, characterized by an outgrowth of Firmicutes by week 8 in all groups except the HPD. MaAsLin2 analysis corroborates this finding and emphasizes an apparent inversion of the microbiome composition at week 8 after HPD. Explicit modification of oncogenic inflammatory biomarkers and fecal microbiome post high FA and protein intake along with voluntary exercise contributed to current underlying evidence that this diet and exercise relationship has broader effects on human health and disease-perhaps importantly as a practical modulation of cancer progression and declining neurocognition.

5.
Int IEEE EMBS Conf Neural Eng ; 2021: 1083-1086, 2021 May.
Artículo en Inglés | MEDLINE | ID: mdl-34909125

RESUMEN

Although vagus nerve stimulation (VNS) can be used to reduce heartrate by enhancing parasympathetic activity, a fully controllable intervention would also require a method for downregulating parasympathetic activity. A direct current (DC) block can be applied to a nerve to block its action potential conduction. This nerve block can be used to downregulate parasympathetic activity by blocking afferent reflexes. The damaging effects of reactions that occur at the electrode-nerve interface using conventional platinum electrodes can be avoided by separating the electrode from the nerve. Using a biocompatible, ionically conducting medium, the electrode and the damaging reactions can be isolated in a vessel away from the nerve. This type of electrode has been called the Separated Interface Nerve Electrode (SINE). Fuzzy logic control (FLC) is a controller approach that is well suited to physiological systems. The SINE, controlled by an FLC, was utilized to block a stimulated vagus nerve and regulate heart rate. The FLC was able to maintain the heartrate at a pre-determined setpoint while still achieving instant recovery when the block was removed.

6.
Anal Methods ; 13(26): 2915-2925, 2021 07 14.
Artículo en Inglés | MEDLINE | ID: mdl-34109341

RESUMEN

Homocysteine, cysteine, cysteinyl-glycine, and glutathione are significant biological aminothiols (ATs) that are marker-molecules in Down syndrome, Alzheimer's disease, or have been implicated as risk factors in atherosclerosis and other vascular diseases, and therefore rapid determination of these molecules is desirable. After reduction of the disulfides, a widely used method utilizes derivatization with ammonium 7-fluorobenzo-2-oxa-1,3-diazole-4-sulfonate (SBD-F) as a fluorogenic probe prior to reversed-phase HPLC separation followed by fluorescence detection. The traditional HPLC determination of ATs is time consuming and economically expensive. We have developed an ion-pair HPLC method coupled with indirect fluorescence detection after post-column reaction with a 2,4-dinitrobenzenesulfonate derivative of a 3-hydroxyflavone. The accuracy, precision, post-column temperature and residence time, and limit-of-detection were evaluated. Sample throughput and reduced sample preparation time of over an hour for the existing methods to less than 20 minutes for the new method is also demonstrated. No statistical differences in HCy, Cys, or Cys-Gly determinations in plasma samples were observed between our method and the traditional HPLC method.


Asunto(s)
Colorantes Fluorescentes , Compuestos de Sulfhidrilo , Cromatografía Líquida de Alta Presión , Cisteína , Flavonoides
7.
PeerJ ; 7: e8240, 2019.
Artículo en Inglés | MEDLINE | ID: mdl-31976165

RESUMEN

Seabirds are highly vocal on land where acoustic communication plays a crucial role in reproduction. Yet, seabirds spend most of their life at sea. They have developed a number of morphological, physiological and behavioural adaptations to forage in the marine environment. The use of acoustic signals at sea could potentially enhance seabirds' foraging success, but remains largely unexplored. Penguins emit vocalisations from the sea surface when commuting, a behaviour possibly associated with group formation at sea. Still, they are unique in their exceptional diving abilities and feed entirely underwater. Other air-breathing marine predators that feed under water, like cetaceans, pinnipeds and marine turtles, are known to emit sound underwater, but such behaviour has not yet been described in seabirds. We aimed to assess the potential prevalence and diversity of vocalisations emitted underwater by penguins. We chose three study species from three different genera, and equipped foraging adults with video cameras with built-in microphones. We recorded a total of 203 underwater vocalisation from all three species during 4 h 43 min of underwater footage. Vocalisations were very short in duration (0.06 s on average), with a frequency of maximum amplitude averaging 998 Hz, 1097 Hz and 680 Hz for King, Gentoo and Macaroni penguins, respectively. All vocalisations were emitted during feeding dives and more than 50% of them were directly associated with hunting behaviour, preceeded by an acceleration (by 2.2 s on average) and/or followed by a prey capture attempt (after 0.12 s on average). The function of these vocalisations remain speculative. Although it seems to be related to hunting behaviour, these novel observations warrant further investigation.

8.
PLoS One ; 13(3): e0194091, 2018.
Artículo en Inglés | MEDLINE | ID: mdl-29584746

RESUMEN

One of the main central processes affecting the cortical representation of conspecific vocalizations is the collateral output from the extended motor system for call generation. Before starting to study this interaction we sought to compare the characteristics of calls produced by stimulating four different parts of the brain in guinea pigs (Cavia porcellus). By using anaesthetised animals we were able to reposition electrodes without distressing the animals. Trains of 100 electrical pulses were used to stimulate the midbrain periaqueductal grey (PAG), hypothalamus, amygdala, and anterior cingulate cortex (ACC). Each structure produced a similar range of calls, but in significantly different proportions. Two of the spontaneous calls (chirrup and purr) were never produced by electrical stimulation and although we identified versions of chutter, durr and tooth chatter, they differed significantly from our natural call templates. However, we were routinely able to elicit seven other identifiable calls. All seven calls were produced both during the 1.6 s period of stimulation and subsequently in a period which could last for more than a minute. A single stimulation site could produce four or five different calls, but the amygdala was much less likely to produce a scream, whistle or rising whistle than any of the other structures. These three high-frequency calls were more likely to be produced by females than males. There were also differences in the timing of the call production with the amygdala primarily producing calls during the electrical stimulation and the hypothalamus mainly producing calls after the electrical stimulation. For all four structures a significantly higher stimulation current was required in males than females. We conclude that all four structures can be stimulated to produce fictive vocalizations that should be useful in studying the relationship between the vocal motor system and cortical sensory representation.


Asunto(s)
Encéfalo/fisiología , Estimulación Acústica/métodos , Animales , Percepción Auditiva/fisiología , Estimulación Eléctrica/métodos , Femenino , Cobayas , Masculino , Neuronas/fisiología , Vocalización Animal/fisiología
9.
Sci Rep ; 7(1): 8185, 2017 08 15.
Artículo en Inglés | MEDLINE | ID: mdl-28811506

RESUMEN

Inducible phenotypic responses to environmental variation are ubiquitous across the tree of life, but it remains an open question whether amphibian chemical defense phenotypes are inducible. Tetrodotoxin (TTX) is a key chemical defense trait in North American and Eurasian newts (Salamandridae). We tested if TTX can be induced by exposing populations of adult and larval California newts (Taricha torosa) to sustained stressful conditions while longitudinally quantifying TTX concentrations. Adult newts rapidly increased chemical defenses in response to simulated predator attacks and consistently maintained elevated TTX concentrations relative to wild, non-captive individuals. We also found that laboratory-reared larvae maintained chemical defenses nearly three-fold greater than those of siblings reared in streams. Collectively, our results indicate that amphibian chemical defenses are not fixed. Instead, toxins are maintained at a baseline concentration that can quickly be increased in response to perceived risk with substantial increases to toxicity. Therefore, it is crucial that inducible variation be accounted for when considering ecological dynamics of chemically defended animals and coevolutionary predator-prey and mimic-model relationships.


Asunto(s)
Anfibios/fisiología , Resistencia a la Enfermedad , Estadios del Ciclo de Vida , Fenotipo , Adaptación Biológica , Animales , California , Ambiente , Larva , Masculino , Carácter Cuantitativo Heredable , Salamandridae/fisiología , Estrés Fisiológico , Tetrodotoxina/farmacología , Tetrodotoxina/toxicidad
10.
J Neurosci ; 37(32): 7759-7771, 2017 08 09.
Artículo en Inglés | MEDLINE | ID: mdl-28706081

RESUMEN

In childhood, partial hearing loss can produce prolonged deficits in speech perception and temporal processing. However, early therapeutic interventions targeting temporal processing may improve later speech-related outcomes. Gap detection is a measure of auditory temporal resolution that relies on the auditory cortex (ACx), and early auditory deprivation alters intrinsic and synaptic properties in the ACx. Thus, early deprivation should induce deficits in gap detection, which should be reflected in ACx gap sensitivity. We tested whether earplugging-induced, early transient auditory deprivation in male and female Mongolian gerbils caused correlated deficits in behavioral and cortical gap detection, and whether these could be rescued by a novel therapeutic approach: brief exposure to gaps in background noise. Two weeks after earplug removal, animals that had been earplugged from hearing onset throughout auditory critical periods displayed impaired behavioral gap detection thresholds (GDTs), but this deficit was fully reversed by three 1 h sessions of exposure to gaps in noise. In parallel, after earplugging, cortical GDTs increased because fewer cells were sensitive to short gaps, and gap exposure normalized this pattern. Furthermore, in deprived animals, both first-spike latency and first-spike latency jitter increased, while spontaneous and evoked firing rates decreased, suggesting that deprivation causes a wider range of perceptual problems than measured here. These cortical changes all returned to control levels after gap exposure. Thus, brief stimulus exposure, perhaps in a salient context such as the unfamiliar placement into a testing apparatus, rescued impaired gap detection and may have potential as a remediation tool for general auditory processing deficits.SIGNIFICANCE STATEMENT Hearing loss in early childhood leads to impairments in auditory perception and language processing that can last well beyond the restoration of hearing sensitivity. Perceptual deficits can be improved by training, or by acoustic enrichment in animal models, but both approaches involve extended time and effort. Here, we used a novel remediation technique, brief periods of auditory stimulus exposure, to fully remediate cortical and perceptual deficits in gap detection induced by early transient hearing loss. This technique also improved multiple cortical response properties. Rescue by this efficient exposure regime may have potential as a therapeutic tool to remediate general auditory processing deficits in children with perceptual challenges arising from early hearing loss.


Asunto(s)
Estimulación Acústica/métodos , Corteza Auditiva/fisiología , Corteza Auditiva/fisiopatología , Percepción Auditiva/fisiología , Potenciales Evocados Auditivos del Tronco Encefálico/fisiología , Pérdida Auditiva/fisiopatología , Factores de Edad , Animales , Femenino , Gerbillinae , Masculino
11.
Nat Commun ; 8: 15961, 2017 06 22.
Artículo en Inglés | MEDLINE | ID: mdl-28639623

RESUMEN

Quasicrystals possess long-range order but lack the translational symmetry of crystalline solids. In solid state physics, periodicity is one of the fundamental properties that prescribes the electronic band structure in crystals. In the absence of periodicity and the presence of quasicrystalline order, the ways that electronic states change remain a mystery. Scanning tunnelling microscopy and atomic manipulation can be used to assemble a two-dimensional quasicrystalline structure mapped upon the Penrose tiling. Here, carbon monoxide molecules are arranged on the surface of Cu(111) one at a time to form the potential landscape that mimics the ionic potential of atoms in natural materials by constraining the electrons in the two-dimensional surface state of Cu(111). The real-space images reveal the presence of the quasiperiodic order in the electronic wave functions and the Fourier analysis of our results links the energy of the resonant states to the local vertex structure of the quasicrystal.

12.
Food Sci Nutr ; 5(1): 38-45, 2017 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-28070314

RESUMEN

In the last several decades, obesity rates have reached epidemic proportions, and increases the risk for a host of comorbidities, including diabetes, cardiovascular disease, and certain kinds of cancers. Boba milk tea, first became popular in the 1990s throughout Asia, and has gained more popularity in the United States and in Europe since 2000. Currently, available nutrition data from online sites suggest this beverage contains high amounts of sugar and fat. One published nutrition study suggests that boba tea drinks are part of the larger group of sugar-sweetened beverages (SSB) because these beverages are usually sweetened with high-fructose corn syrup (HFCS). This study experimentally determined the sugar composition (sucrose, fructose, glucose, and melezitose) and calorific values of boba milk tea drinks and their components. Results suggested that boba drinks fit the US Dietary Guidelines definition of a SSB. One 16-ounce boba drink exceeds the upper limit of added sugar intake recommended by the 2015 US Dietary Guidelines Advisory Committee. The high caloric and sugar content of boba beverages pose public health concerns as they have the potential to further exacerbate the childhood obesity epidemic. Nutrition education targeting Asian populations should give special attention to boba tea as a SSB. Also, prudent public health recommendations should be suggested for moderate consumption of these beverages. With the growing popularity of boba beverages in the United States, the findings from this study provide public health practitioners with valuable data on how boba beverages compare with other SSBs.

13.
Front Neurosci ; 10: 263, 2016.
Artículo en Inglés | MEDLINE | ID: mdl-27378837

RESUMEN

Perceptual learning (training-induced performance improvement) can be elicited by task-irrelevant stimulus exposure in humans. In contrast, task-irrelevant stimulus exposure in animals typically disrupts perception in juveniles while causing little to no effect in adults. This may be due to the extent of exposure, which is brief in humans while chronic in animals. Here we assessed the effects of short bouts of passive stimulus exposure on learning during development in gerbils, compared with non-passive stimulus exposure (i.e., during testing). We used prepulse inhibition of the acoustic startle response, a method that can be applied at any age, to measure gap detection thresholds across four age groups, spanning development. First, we showed that both gap detection thresholds and gap detection learning across sessions displayed a long developmental trajectory, improving throughout the juvenile period. Additionally, we demonstrated larger within- and across-animal performance variability in younger animals. These results are generally consistent with results in humans, where there are extended developmental trajectories for both the perception of temporally-varying signals, and the effects of perceptual training, as well as increased variability and poorer performance consistency in children. We then chose an age (mid-juveniles) that displayed clear learning over sessions in order to assess effects of brief passive stimulus exposure on this learning. We compared learning in mid-juveniles exposed to either gap detection testing (gaps paired with startles) or equivalent gap exposure without testing (gaps alone) for three sessions. Learning was equivalent in both these groups and better than both naïve age-matched animals and controls receiving no gap exposure but only startle testing. Thus, short bouts of exposure to gaps independent of task performance is sufficient to induce learning at this age, and is as effective as gap detection testing.

14.
Proc Biol Sci ; 283(1831)2016 05 25.
Artículo en Inglés | MEDLINE | ID: mdl-27194704

RESUMEN

Behaviours that influence habitat selection strongly determine species movement patterns. One component of animal behaviour that largely influences movement patterns and habitat choice is site fidelity. California newts (family Salamandridae) demonstrate remarkable site fidelity, typically homing to the same pool of a stream each breeding season. Individuals often occupy a specific pool throughout the breeding season, but some males shift among breeding pools, altering their set of potential mates, competitors, and predators. In this study, we measured dermal concentrations of the chemical defence compound tetrodotoxin (TTX) in recaptured male California newts (Taricha torosa) over five breeding seasons to evaluate whether relative TTX concentrations are associated with breeding site fidelity in the field. Our five years of field sampling indicates that TTX concentrations of individuals and group means fluctuate tremendously, implying that TTX is not a stable phenotypic trait. Despite such fluctuations, we found that an individual's relative TTX concentration explains fidelity to a breeding pool and suggests that newts may be able to assess both their own concentrations of TTX and that of conspecifics to make decisions about remaining in or abandoning a breeding pool. These results provide us a novel dimension to chemical defence phenotypes in nature and their ecological consequences, potentially requiring a re-evaluation of the coevolutionary dynamics of predation pressure on toxin-laden organisms.


Asunto(s)
Ecosistema , Salamandridae/fisiología , Tetrodotoxina/metabolismo , Animales , California , Masculino , Reproducción
15.
J Lesbian Stud ; 19(3): 317-35, 2015.
Artículo en Inglés | MEDLINE | ID: mdl-26075686

RESUMEN

This article argues that love and justice are interlocking themes that undergird and motivate the poetry and activism of the Black lesbian feminist Pat Parker. Parker was a prolific working-class poet, a committed Black lesbian feminist, and an international trailblazer whose poems, like her famous "Womanslaughter" discussed in this article, document the many injustices that Black women endured in an anti-Black, rabidly homophobic, and patriarchal U.S. during the last decades of the twentieth century. In a political moment where righteous cries of #BlackLivesMatter are heard across the United States I use this article to remind us all of the historical importance that Black lesbians played and continue to play in the struggles of anti-racist justice in America.


Asunto(s)
Población Negra/historia , Feminismo/historia , Homosexualidad Femenina/historia , Poesía como Asunto/historia , Justicia Social/historia , Femenino , Amigos , Historia del Siglo XX , Humanos , Percepción Social , Estados Unidos
16.
Dalton Trans ; 43(43): 16498-508, 2014 Nov 21.
Artículo en Inglés | MEDLINE | ID: mdl-25256407

RESUMEN

Eight bis-ligated, homoleptic, zinc complexes were synthesized through the reaction of NNO Schiff base ketoimines bearing varying substituents with diethyl zinc in an inert atmosphere glovebox at room temperature and isolated in 62-95% yield. The complexes were characterized with (1)H, (13)C, and (19)F nuclear magnetic resonance spectroscopy, absorbance spectroscopy, high resolution mass spectrometry, elemental analysis, and single crystal X-ray crystallography. The complexes were shown to adopt distorted octahedral coordination geometry around zinc. The (1)H and (19)F NMR spectra of complexes 1-7 showed stable zinc coordination at 300 K while the effect of steric encumbrance and two trifluoromethyl groups in complex 8 was investigated with variable temperature NMR. The bis-ligated zinc complexes were effective initiators for the ring opening polymerization of L-lactide into poly-L-lactic acid (PLLA). With [L-lac]/[Zn complex] = 50, the bis-ligated zinc complexes yielded percentage conversion of 14-98% with polymerization times varying from 15-1440 min, where the longest reaction times were required when two trifluoromethyl groups were present. The addition of 4-fluorophenol co-catalyst resulted in up to a 5-fold increase in the percentage conversion in toluene solution and up to a 14-fold increase in bulk melt polymerization with reductions in the poly-dispersity index values for the isolated PLLA. Addition of 4-fluorophenol to complex 1 was studied with (1)H and (19)F NMR and appeared to yield an in situ generated zinc alkoxide complex.


Asunto(s)
Complejos de Coordinación/química , Dioxanos/química , Iminas/química , Zinc/química , Complejos de Coordinación/síntesis química , Cristalografía por Rayos X , Ácido Láctico/química , Espectroscopía de Resonancia Magnética , Conformación Molecular , Poliésteres , Polimerizacion , Polímeros/química , Espectrometría de Masa por Láser de Matriz Asistida de Ionización Desorción
17.
Toxicon ; 80: 87-93, 2014 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-24467994

RESUMEN

Toxic or noxious substances often serve as a means of chemical defense for numerous taxa. However, such compounds may also facilitate ecological or evolutionary processes. The neurotoxin, tetrodotoxin (TTX), which is found in newts of the genus Taricha, acts as a selection pressure upon predatory garter snakes, is a chemical cue to conspecific larvae, which elicits antipredator behavior, and may also affect macroinvertebrate foraging behavior. To understand selection patterns and how potential variation might affect ecological and evolutionary processes, it is necessary to quantify TTX levels within individuals and populations. To do so has often required that animals be destructively sampled or removed from breeding habitats and brought into the laboratory. Here we demonstrate a non-destructive method of sampling adult Taricha that obviates the need to capture and collect individuals. We also show that embryos from oviposited California newt (Taricha torosa) egg masses can be individually sampled and TTX quantified from embryos. We employed three different extraction techniques to isolate TTX. Using a custom fabricated high performance liquid chromatography (HPLC) system we quantified recovery of TTX. We found that a newly developed micro-extraction technique significantly improved recovery compared to previously used methods. Results also indicate our improvements to the HPLC method have high repeatability and increased sensitivity, with a detection limit of 48 pg (0.15 pmol) TTX. The quantified amounts of TTX in adult newts suggest fine geographic variation in toxin levels between sampling localities isolated by as little as 3 km.


Asunto(s)
Cromatografía Líquida de Alta Presión/métodos , Salamandridae , Tetrodotoxina/análisis , Animales , Evolución Biológica , California , Colubridae , Larva/química , Masculino , Óvulo/química , Conducta Predatoria , Piel/química
18.
PLoS One ; 9(12): e116544, 2014.
Artículo en Inglés | MEDLINE | ID: mdl-25551620

RESUMEN

During breeding, animal behaviour is particularly sensitive to environmental and food resource availability. Additionally, factors such as sex, body condition, and offspring developmental stage can influence behaviour. Amongst seabirds, behaviour is generally predictably affected by local foraging conditions and has therefore been suggested as a potentially useful proxy to indicate prey state. However, besides prey availability and distribution, a range of other variables also influence seabird behavior, and these need to be accounted for to increase the signal-to-noise ratio when assessing specific characteristics of the environment based on behavioural attributes. The aim of this study was to use continuous, fine-scale time-activity budget data from a pelagic seabird (Cape gannet, Morus capensis) to determine the influence of intrinsic (sex and body condition) and extrinsic (offspring and time) variables on parent behaviour during breeding. Foraging trip duration and chick provisioning rates were clearly sex-specific and associated with chick developmental stage. Females made fewer, longer foraging trips and spent less time at the nest during chick provisioning. These sex-specific differences became increasingly apparent with chick development. Additionally, parents in better body condition spent longer periods at their nests and those which returned later in the day had longer overall nest attendance bouts. Using recent technological advances, this study provides new insights into the foraging behaviour of breeding seabirds, particularly during the post-guarding phase. The biparental strategy of chick provisioning revealed in this study appears to be an example where the costs of egg development to the female are balanced by paternal-dominated chick provisioning particularly as the chick nears fledging.


Asunto(s)
Conducta Animal , Aves/fisiología , Animales , Aves/anatomía & histología , Tamaño Corporal , Cruzamiento , Conducta Alimentaria , Femenino , Masculino , Comportamiento de Nidificación , Factores Sexuales , Conducta Sexual Animal , Sudáfrica , Factores de Tiempo
19.
Talanta ; 100: 384-90, 2012 Oct 15.
Artículo en Inglés | MEDLINE | ID: mdl-23141353

RESUMEN

The present study reports an improved method to quickly and reproducibly isolate the saccharides from a variety of dairy and soy products utilizing reversed-phase solid-phase extraction to quantitatively remove fats, fatty acids, and lipids followed by desalination and deproteinization by ion-exchange solid-phase extraction with no loss of saccharides during extraction. Analysis of the isolated saccharides was performed by ligand-exchange HPLC. The method presented requires no prolonged heating (thus protecting the saccharides from hydrolysis or isomerization), uses benign reagents, and realizes a significant time savings over existing methods. The isolation and analysis of monosaccharides (glucose, galactose and fructose), disaccharides (lactose and sucrose), and polysaccharides (raffinose and stachyose) from dairy products (whole, reduced fat, and lactose-free milk and yogurt), infant formula (powdered and premixed), and soy beverages were studied in this investigation with recoveries ranging from 88% to 110% in all products studied. We also applied the method to quickly discriminate authentic soy milk from a soy beverage, branded as soy milk.


Asunto(s)
Carbohidratos/aislamiento & purificación , Cromatografía Líquida de Alta Presión/métodos , Productos Lácteos/análisis , Extracción en Fase Sólida/métodos , Alimentos de Soja/análisis , Carbohidratos/análisis , Carbohidratos/química , Ácidos Grasos/química , Ácidos Grasos/aislamiento & purificación , Intercambio Iónico , Isomerismo , Ligandos , Proteínas de la Leche/química , Proteínas de la Leche/aislamiento & purificación , Sales (Química)/química , Sales (Química)/aislamiento & purificación , Leche de Soja/química , Proteínas de Soja/química , Proteínas de Soja/aislamiento & purificación , Triglicéridos/química , Triglicéridos/aislamiento & purificación
20.
Anal Bioanal Chem ; 399(10): 3589-600, 2011 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-21274517

RESUMEN

Volatile organic compounds emitted from a several decade series of bound periodicals (1859-1939) printed on ground wood paper, as well as historical books dating from the 1500s to early 1800s made from cotton/linen rag, were studied using an improved headspace SPME/GC-MS method. The headspace over the naturally aging books, stored upright in glass chambers, was monitored over a 24-h period, enabling the identification of a wide range of organic compounds emanating from the whole of the book. The detection of particular straight chain aldehydes, as well as characteristic alcohols, alkenes and ketones is correlated with oxidative degradation of the C(18) fatty acid constituency of paper. The relative importance of hydrolytic and oxidative chemistry involved in paper aging in books published between 1560 and 1939 was examined by comparing the relative abundances of furfural (FUR) a known cellulose hydrolysis product, and straight chain aldehydes (SCA) produced from the oxidation of fatty acids in paper. The relative abundance of furfural is shown to increase across the 379-year publication time span. A comparison of relative SCA peak areas across the series of books examined reveals that SCA emission is more important in the cotton/linen rag books than in the ground wood books.


Asunto(s)
Libros , Celulosa/química , Ácidos Grasos/química , Cromatografía de Gases y Espectrometría de Masas/métodos , Microextracción en Fase Sólida/métodos , Libros/historia , Historia del Siglo XVI , Historia del Siglo XVII , Historia del Siglo XVIII , Historia del Siglo XIX , Historia del Siglo XX , Hidrólisis , Oxidación-Reducción
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