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1.
J Neurophysiol ; 2024 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-38919149

RESUMO

Previous research has shown that action effects of self-generated movements are internally predicted before outcome feedback becomes available. To test whether these sensorimotor predictions are used to facilitate visual information uptake for feedback processing, we measured eye movements during the execution of a goal-directed throwing task. Participants could fully observe the effects of their throwing actions (ball trajectory, and either hitting or missing a target) in most of the trials. In a portion of the trials, the ball trajectory was not visible, and participants only received static information about the outcome. We observed a large proportion of predictive saccades, shifting gaze toward the goal region before the ball arrived and outcome feedback became available. Fixation locations after predictive saccades systematically covaried with future ball positions in trials with continuous ball flight information, but notably also in trials with static outcome feedback and only efferent and proprioceptive information about the movement that could be used for predictions. Fixation durations at the chosen positions after feedback onset were modulated by action outcome (longer durations for misses than for hits) and outcome uncertainty (longer durations for narrow vs. clear outcomes). Combining both effects, durations were longest for narrow errors and shortest for clear hits, indicating that the chosen locations offer informational value for feedback processing. Thus, humans are able to use sensorimotor predictions to direct their gaze toward task-relevant feedback locations. Outcome-dependent saccade latency differences (miss vs. hit) indicate that also predictive valuation processes are involved in planning predictive saccades.

2.
J Neurophysiol ; 129(3): 717-732, 2023 03 01.
Artigo em Inglês | MEDLINE | ID: mdl-36791071

RESUMO

Motor adaptation maintains movement accuracy. To evaluate movement accuracy, motor adaptation relies on an error signal, generated by the movement target, while suppressing error signals from irrelevant objects in the vicinity. Previous work used static testing environments, where all information required to evaluate movement accuracy was available simultaneously. Using saccadic eye movements as a model for motor adaptation, we tested how movement accuracy is maintained in dynamic environments, where the availability of conflicting error signals varied over time. Participants made a vertical saccade toward a target (either a small square or a large ring). Upon saccade detection, two candidate stimuli were shown left and right of the target, and participants were instructed to discriminate a feature on one of the candidates. Critically, candidate stimuli were presented sequentially, and saccade adaptation, thus, had to resolve a conflict between a task-relevant and a task-irrelevant error signal that were separated in space and time. We found that the saccade target influenced several aspects of oculomotor learning. In presence of a small target, saccade adaptation evaluated movement accuracy based on the first available error signal after the saccade, irrespective of its task relevance. However, a large target not only allowed for greater flexibility when evaluating movement accuracy, but it also promoted a stronger contribution of strategic behavior when compensating inaccurate saccades. Our results demonstrate how motor adaptation maintains movement accuracy in dynamic environments, and how properties of the visual environment modulate the relative contribution of different learning processes.NEW & NOTEWORTHY Motor adaptation is typically studied in static environments, where all information that is required to evaluate movement accuracy is available simultaneously. Here, using saccadic eye movements as a model, we studied motor adaptation in a dynamic environment, where the availability of conflicting information about movement accuracy varied over time. We demonstrate that properties of the visual environment determine how dynamic movement errors are corrected.


Assuntos
Movimentos Oculares , Movimentos Sacádicos , Humanos , Adaptação Fisiológica , Movimento , Aprendizagem
3.
Ann Pharmacother ; 57(2): 141-147, 2023 02.
Artigo em Inglês | MEDLINE | ID: mdl-35658717

RESUMO

BACKGROUND: Vasoplegic shock occurs in up to 37% of cardiac surgery patients. We investigated the use of angiotensin II for treating vasoplegic shock in these patients. OBJECTIVES: We assessed clinical outcomes and mortality in patients undergoing cardiac surgery at our center between March 1, 2018 and October 31, 2020 who developed vasoplegic shock, comparing those who received angiotensin II with those who did not. METHODS: This was a retrospective chart review. Response to angiotensin II was defined as increase in or maintenance of mean arterial pressure (MAP) and decrease in background vasopressor dosage. RESULTS: Angiotensin II was administered to 7 patients (postoperatively in 4 patients [57.1%]) with vasoplegic shock and baseline norepinephrine equivalent (NEE) of 0.49 ± 0.08 µg/kg/min; 12 patients with vasoplegic shock did not receive angiotensin II. Within 3 hours of angiotensin II administration, NEE decreased by 38.0 ± 33.1%. Angiotensin patients were more likely to newly require renal replacement therapy (66.7% vs 9.1%, P = 0.03) and had a longer, although not statistically significant, postoperative stay (23.1 vs 14.0 days, P = 0.16). Despite higher NEE requirements at baseline (0.49 vs 0.30, P = 0.03) and over the next 48 hours in the angiotensin group, no between-group differences in 7-day mortality (14.3% vs 0.0%, P = 0.37) or 30-day mortality (28.6% vs 8.3%, P = 0.52) were noted. CONCLUSION AND RELEVANCE: In patients who developed vasoplegic shock after cardiac surgery, angiotensin II administration allowed immediate dosage reductions of other vasopressors while maintaining MAP. Despite its small sample size, this study adds to the paucity of data in these patients and highlights future research needs.


Assuntos
Procedimentos Cirúrgicos Cardíacos , Choque , Veteranos , Humanos , Angiotensina II , Estudos Retrospectivos , Choque/tratamento farmacológico , Procedimentos Cirúrgicos Cardíacos/efeitos adversos , Vasoconstritores/uso terapêutico , Norepinefrina/uso terapêutico
4.
J Vis ; 23(2): 1, 2023 02 01.
Artigo em Inglês | MEDLINE | ID: mdl-36723930

RESUMO

The perceptual representation of our environment does not only involve what we actually can see, but also inferences about what is hidden from our sight. For example, in amodal completion, simple contours or surfaces are filled-in behind occluding objects allowing for a complete representation. This is important for many everyday tasks, such as visual search, foraging, and object handling. Although there is support for completion of simple patterns from behavioral and neurophysiological studies, it is unclear if these mechanisms extend to complex, irregular patterns. Here, we show that the number of hidden objects on partially occluded surfaces is underestimated. Observers did not consider accurately the number of visible objects and the proportion of occlusion to infer the number of hidden objects, although these quantities were perceived accurately and reliably. However, visible objects were not simply ignored: estimations of hidden objects increased when the visible objects formed a line across the occluder and decreased when the visible objects formed a line outside of the occluder. Confidence ratings for numerosity estimation were similar for fully visible and partially occluded surfaces. These results suggest that perceptual inferences about what is hidden in our environment can be very inaccurate und underestimate the complexity of the environment.


Assuntos
Percepção de Forma , Humanos
5.
J Med Syst ; 46(12): 94, 2022 Nov 11.
Artigo em Inglês | MEDLINE | ID: mdl-36367614

RESUMO

In this brief communication, we reported Telehealth Home-Based Cardiac Rehabilitation (CR) program structure and preliminary outcomes from patients that completed a 12-week program after coronary artery bypass graft surgery (CABG). We aim to advocate the use of Telerehabilitation as a Phase II CR in patients immediately after the CABG. This approach was innovative and encouraging because the patients were still in subacute phase. The program can serve as a continuation of care for the patients after being discharged from a hospital while regaining their functional ability at home. Our preliminary outcomes demonstrated improvements in resting heart rate, activity level, nutrition status, self-efficacy for managing cardiac diseases, muscle strength, endurance and depression. There were no adverse events during the virtual sessions. Patient satisfaction score was high.


Assuntos
Reabilitação Cardíaca , Telerreabilitação , Humanos , Ponte de Artéria Coronária/reabilitação , Atividades Cotidianas , Força Muscular
6.
Conscious Cogn ; 89: 103086, 2021 03.
Artigo em Inglês | MEDLINE | ID: mdl-33550190

RESUMO

Individuals are often confronted with events that violate their expectations, but disconfirming evidence does not always lead to expectation change. We review seven theoretical models on how individuals cope with disconfirming expectations: associative learning theories, the ViolEx Model, the model of coping with expectation disconfirmation (Roese & Sherman, 2007), the Meaning Maintenance Model, the Predictive Processing Framework, Expectancy Violations Theory, and the Expectation-Disconfirmation Model of consumer satisfaction. We focus on the proposed processes that relate to persistence or change of expectations. We discuss similarities and differences between the models. Three core coping processes are identified across most of these models - minimization of the importance of expectation-disconfirming evidence, search for/production of future expectation-confirming evidence, and expectation change. Suggestions for refinements and extensions of the models as well as for future empirical work on model testing are drawn.


Assuntos
Adaptação Psicológica , Motivação , Atenção , Humanos
7.
Perception ; 50(4): 343-366, 2021 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-33840288

RESUMO

A major objective of perception is the reduction of uncertainty about the outside world. Eye-movement research has demonstrated that attention and oculomotor control can subserve the function of decreasing uncertainty in vision. Here, we ask whether a similar effect exists for awareness in binocular rivalry, when two distinct stimuli presented to the two eyes compete for awareness. We tested whether this competition can be biased by uncertainty about the stimuli and their relevance for a perceptual task. Specifically, we have stimuli that are perceptually difficult (i.e., carry high perceptual uncertainty) compete with stimuli that are perceptually easy (low perceptual uncertainty). Using a no-report paradigm and reading the dominant stimulus continuously from the observers' eye movements, we find that the perceptually difficult stimulus becomes more dominant than the easy stimulus. This difference is enhanced by the stimuli's relevance for the task. In trials with task, the difference in dominance emerges quickly, peaks before the response, and then persists throughout the trial (further 10 s). However, the difference is already present in blocks before task instruction and still observable when the stimuli have ceased to be task relevant. This shows that perceptual uncertainty persistently increases perceptual dominance, and this is magnified by task relevance.


Assuntos
Atenção , Visão Binocular , Olho , Movimentos Oculares , Humanos , Sensação
8.
Proc Natl Acad Sci U S A ; 115(9): 2240-2245, 2018 02 27.
Artigo em Inglês | MEDLINE | ID: mdl-29440494

RESUMO

Due to the foveal organization of our visual system we have to constantly move our eyes to gain precise information about our environment. Doing so massively alters the retinal input. This is problematic for the perception of moving objects, because physical motion and retinal motion become decoupled and the brain has to discount the eye movements to recover the speed of moving objects. Two different types of eye movements, pursuit and saccades, are combined for tracking. We investigated how the way we track moving targets can affect the perceived target speed. We found that the execution of corrective saccades during pursuit initiation modifies how fast the target is perceived compared with pure pursuit. When participants executed a forward (catch-up) saccade they perceived the target to be moving faster. When they executed a backward saccade they perceived the target to be moving more slowly. Variations in pursuit velocity without corrective saccades did not affect perceptual judgments. We present a model for these effects, assuming that the eye velocity signal for small corrective saccades gets integrated with the retinal velocity signal during pursuit. In our model, the execution of corrective saccades modulates the integration of these two signals by giving less weight to the retinal information around the time of corrective saccades.


Assuntos
Percepção de Movimento , Estimulação Luminosa , Movimentos Sacádicos/fisiologia , Adulto , Encéfalo/fisiologia , Feminino , Fóvea Central , Humanos , Masculino , Movimento (Física) , Distribuição Normal , Reprodutibilidade dos Testes , Retina/fisiologia , Adulto Jovem
9.
J Vis ; 21(6): 11, 2021 06 07.
Artigo em Inglês | MEDLINE | ID: mdl-34144606

RESUMO

Saccadic eye movements modulate visual perception: they initiate and terminate high acuity vision at a certain location in space, but before and during their execution visual contrast sensitivity is strongly attenuated for 100 to 200 ms. Transient perisaccadic perceptual distortions are assumed to be an important mechanism to maintain visual stability. Little is known about age effects on saccadic suppression, even though for healthy adults other major age-related changes are well documented, like a decrease of visual contrast sensitivity for intermediate and high spatial frequencies or an increase of saccade latencies. Here, we tested saccadic suppression of luminance and isoluminant chromatic flashes in 100 participants from eight to 78 years. To estimate the effect of saccadic suppression on contrast sensitivity, we used a two-alternative forced choice (2AFC) design and an adaptive staircase procedure to modulate the luminance or chromatic contrast of a flashed detection target during fixation and 15 ms after saccade onset. The target was a single horizontal luminance or chromatic line flashed 2° above or below the fixation or saccade target. Compared to fixation, average perisaccadic contrast sensitivity decreased significantly by 66% for luminance and by 36% for color. A significant correlation was found for the strength of saccadic suppression of luminance and color. However, a small age effect was found only for the strength of saccadic suppression of luminance, which increased from 64% to 70% from young to old age. We conclude that saccadic suppression for luminance and color is present in most participants independent of their age and that mechanisms of suppression stay relatively stable during healthy aging.


Assuntos
Movimentos Sacádicos , Percepção Visual , Adulto , Sensibilidades de Contraste , Humanos , Estimulação Luminosa , Visão Ocular
10.
J Vis ; 20(12): 3, 2020 11 02.
Artigo em Inglês | MEDLINE | ID: mdl-33156337

RESUMO

Previous studies revealed that there are idiosyncratic preferences to perceive certain motion directions in front during motion transparency depth rivalry (Mamassian & Wallace, 2010; Schütz, 2014). Meanwhile, other studies reported idiosyncratic preferences in binocular rivalry during the onset stage (Carter & Cavanagh, 2007; Stanley, Carter, & Forte, 2011). Here we investigated the relationship of idiosyncratic preferences in transparent motion and binocular rivalry. We presented two dot clouds that were moving in opposite directions. In the transparent motion condition, both dot clouds were presented to both eyes and participants had to report the dot cloud they perceived in front. In the binocular rivalry condition, the dot clouds were presented to different eyes and participants had to report the dominant dot cloud. There were strong idiosyncratic directional preferences in transparent motion and rather weak directional preferences in binocular rivalry. In general, binocular rivalry was dominated by biases in contrast polarity, whereas transparent motion was dominated by biases in motion direction. A circular correlation analysis showed no correlation between directional preferences in transparent motion and binocular rivalry. These findings show that idiosyncratic preferences in a visual feature can be dissociated at different stages of processing.


Assuntos
Dominância Ocular/fisiologia , Percepção de Movimento/fisiologia , Visão Binocular/fisiologia , Adulto , Viés , Feminino , Humanos , Masculino , Estimulação Luminosa , Adulto Jovem
11.
J Vis ; 20(10): 13, 2020 10 01.
Artigo em Inglês | MEDLINE | ID: mdl-33052408

RESUMO

Humans do not notice small displacements to objects that occur during saccades, termed saccadic suppression of displacement (SSD), and this effect is reduced when a blank is introduced between the pre- and postsaccadic stimulus (Bridgeman, Hendry, & Stark, 1975; Deubel, Schneider, & Bridgeman, 1996). While these effects have been studied extensively in adults, it is unclear how these phenomena are characterized in children. A potentially related mechanism, saccadic suppression of contrast sensitivity-a prerequisite to achieve a stable percept-is stronger for children (Bruno, Brambati, Perani, & Morrone, 2006). However, the evidence for how transsaccadic stimulus displacements may be suppressed or integrated is mixed. While they can integrate basic visual feature information from an early age, they cannot integrate multisensory information (Gori, Viva, Sandini, & Burr, 2008; Nardini, Jones, Bedford, & Braddick, 2008), suggesting a failure in the ability to integrate more complex sensory information. We tested children 7 to 12 years old and adults 19 to 23 years old on their ability to perceive intrasaccadic stimulus displacements, with and without a postsaccadic blank. Results showed that children had stronger SSD than adults and a larger blanking effect. Children also had larger undershoots and more variability in their initial saccade endpoints, indicating greater intrinsic uncertainty, and they were faster in executing corrective saccades to account for these errors. Together, these results suggest that children may have a greater internal expectation or prediction of saccade error than adults; thus, the stronger SSD in children may be due to higher intrinsic uncertainty in target localization or saccade execution.


Assuntos
Sensibilidades de Contraste/fisiologia , Movimentos Sacádicos/fisiologia , Percepção Visual/fisiologia , Adulto , Criança , Feminino , Humanos , Masculino , Incerteza , Adulto Jovem
12.
J Vis ; 20(12): 2, 2020 11 02.
Artigo em Inglês | MEDLINE | ID: mdl-33141171

RESUMO

Visual processing varies dramatically across the visual field. These differences start in the retina and continue all the way to the visual cortex. Despite these differences in processing, the perceptual experience of humans is remarkably stable and continuous across the visual field. Research in the last decade has shown that processing in peripheral and foveal vision is not independent, but is more directly connected than previously thought. We address three core questions on how peripheral and foveal vision interact, and review recent findings on potentially related phenomena that could provide answers to these questions. First, how is the processing of peripheral and foveal signals related during fixation? Peripheral signals seem to be processed in foveal retinotopic areas to facilitate peripheral object recognition, and foveal information seems to be extrapolated toward the periphery to generate a homogeneous representation of the environment. Second, how are peripheral and foveal signals re-calibrated? Transsaccadic changes in object features lead to a reduction in the discrepancy between peripheral and foveal appearance. Third, how is peripheral and foveal information stitched together across saccades? Peripheral and foveal signals are integrated across saccadic eye movements to average percepts and to reduce uncertainty. Together, these findings illustrate that peripheral and foveal processing are closely connected, mastering the compromise between a large peripheral visual field and high resolution at the fovea.


Assuntos
Fóvea Central/fisiologia , Visão Ocular/fisiologia , Percepção Visual/fisiologia , Humanos , Córtex Visual/fisiologia , Campos Visuais/fisiologia
13.
J Neurophysiol ; 122(4): 1491-1501, 2019 10 01.
Artigo em Inglês | MEDLINE | ID: mdl-31365324

RESUMO

Across saccades, humans can integrate the low-resolution presaccadic information of an upcoming saccade target with the high-resolution postsaccadic information. There is converging evidence to suggest that transsaccadic integration occurs at the saccade target. However, given divergent evidence on the spatial specificity of related mechanisms such as attention, visual working memory, and remapping, it is unclear whether integration is also possible at locations other than the saccade target. We tested the spatial profile of transsaccadic integration, by testing perceptual performance at six locations around the saccade target and between the saccade target and initial fixation. Results show that integration benefits do not differ between the saccade target and surrounding locations. Transsaccadic integration benefits are not specific to the saccade target and can occur at other locations when they are behaviorally relevant, although there is a trend for worse performance for the location above initial fixation compared with those in the direction of the saccade. This suggests that transsaccadic integration may be a more general mechanism used to reconcile task-relevant pre- and postsaccadic information at attended locations other than the saccade target.NEW & NOTEWORTHY This study shows that integration of pre- and postsaccadic information across saccades is not restricted to the saccade target. We found performance benefits of transsaccadic integration at attended locations other than the saccade target, and these benefits did not differ from those found at the saccade target. This suggests that transsaccadic integration may be a more general mechanism used to reconcile pre- and postsaccadic information at task-relevant locations.


Assuntos
Movimentos Sacádicos/fisiologia , Adulto , Feminino , Fixação Ocular , Humanos , Masculino , Desempenho Psicomotor , Comportamento Espacial
14.
Anal Bioanal Chem ; 411(19): 4785-4796, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-30707264

RESUMO

In this work, the multiclass detection of explosives and related compounds has been studied by liquid chromatography-high-resolution mass spectrometry by means of a time-of-flight mass spectrometer (TOFMS) operated in the negative ion mode, using dielectric barrier discharge ionization (DBDI). Reversed-phase high-performance liquid chromatography (HPLC) separation was performed using water-methanol mobile phase without any modifier, although the effect of ammonium acetate was studied. DBD plasma was generated by applying a square wave voltage of 2.5 kV to a 100-mL min-1 He flow. The DBDI probe was adjusted to fit the commercial API source housing so that the HPLC eluent was nebulized and vaporized in the same manner as for atmospheric-pressure chemical ionization (APCI). The ionization process was affected by the temperature of the two nitrogen streams used to vaporize the solvent and the analytes, particularly for RDX and HMX, which are thermolabile compounds. The best approach in terms of sensitivity for all the studied compounds was the use of a gradient of temperatures in the ionization source, starting at 225/200 °C (vaporizer/drying gas temp) for nitramines and ending at 350/325 °C for nitroaromatic compounds. High-resolution full-scan spectra of individual selected compounds were recorded by LC-DBDI-TOFMS, and the results were compared to LC-APCI-TOFMS. A better sensitivity (slope of calibration curve) was obtained by DBDI for more than 70% of the studied compounds in both wastewater and soil extracts. Graphical abstract ᅟ.

15.
J Vis ; 19(14): 26, 2019 12 02.
Artigo em Inglês | MEDLINE | ID: mdl-31880782

RESUMO

What we see is influenced by where we look. When confronted with multiple relevant targets, inaccurate saccade target selection can impair perceptual performance. Here we ask whether endpoint selection can be optimized by the mechanism maintaining saccade accuracy: saccade adaptation. Therefore, we introduce a double-target adaptation task, where a presaccadic peripheral stimulus (plaid) splits vertically into its two components (Gabor patches) during horizontal saccades. While both targets were task-relevant, one of them provided more information for the perceptual task, because it could only be identified after the saccade with near-foveal vision. The other target was highly salient and could also be identified in the presaccadic plaid using peripheral vision. This double-target paradigm induced saccade adaptation: Without a perceptual task, participants adapted to the salient target. When both targets were judged sequentially, participants mostly adapted to the target they had to judge first. When targets were judged simultaneously, endpoints were biased toward the informative target but showed no gradual learning and fell short of optimality. We observed gradual adaptation when targets shifted randomly such that a strategic adjustment of endpoints was not possible. Overall, these findings show that when multiple targets compete, our oculomotor system can learn to adjust endpoints in order to maximize information for perception. Yet individual variability and other factors affecting target priority play a crucial role.


Assuntos
Adaptação Fisiológica , Movimentos Sacádicos , Percepção Espacial , Percepção Visual , Adolescente , Adulto , Feminino , Fóvea Central/fisiologia , Humanos , Masculino , Estimulação Luminosa , Probabilidade , Campos Visuais , Adulto Jovem
16.
J Vis ; 19(6): 17, 2019 06 03.
Artigo em Inglês | MEDLINE | ID: mdl-31206139

RESUMO

Humans are able to integrate pre- and postsaccadic percepts of an object across saccades to maintain perceptual stability. Previous studies have used Maximum Likelihood Estimation (MLE) to determine that integration occurs in a near-optimal manner. Here, we compared three different models to investigate the mechanism of integration in more detail: an early noise model, where noise is added to the pre- and postsaccadic signals before integration occurs; a late-noise model, where noise is added to the integrated signal after integration occurs; and a temporal summation model, where integration benefits arise from the longer transsaccadic presentation duration compared to pre- and postsaccadic presentation only. We also measured spatiotemporal aspects of integration to determine whether integration can occur for very brief stimulus durations, across two hemifields, and in spatiotopic and retinotopic coordinates. Pre-, post-, and transsaccadic performance was measured at different stimulus presentation durations, both at the saccade target and a location where the pre- and postsaccadic stimuli were presented in different hemifields across the saccade. Results showed that for both within- and between-hemifields conditions, integration could occur when pre- and postsaccadic stimuli were presented only briefly, and that the pattern of integration followed an early noise model. Whereas integration occurred when the pre- and post-saccadic stimuli were presented in the same spatiotopic coordinates, there was no integration when they were presented in the same retinotopic coordinates. This contrast suggests that transsaccadic integration is limited by early, independent, sensory noise acting separately on pre- and postsaccadic signals.


Assuntos
Movimentos Sacádicos/fisiologia , Lobo Temporal/fisiologia , Percepção Visual/fisiologia , Adulto , Feminino , Humanos , Masculino , Estimulação Luminosa , Adulto Jovem
17.
Anal Chem ; 90(17): 10111-10116, 2018 09 04.
Artigo em Inglês | MEDLINE | ID: mdl-30063325

RESUMO

Dielectric barrier discharges are used as soft ionization sources for mass spectrometers or ion mobility spectrometers, enabling excellent possibilities for analytical applications. A new robust and small-footprint discharge design, flexible microtube plasma (FµTP), developed as a result of ongoing miniaturization and electrode design processes, is presented in this work. This design provides major safety benefits by fitting the electrode into an inert flexible fused silica capillary (tube). Notably, in this context, the small discharge dimensions enable very low gas flows in the range of <100 mL min-1; portability; the use of hydrogen, nitrogen, and air in addition to noble gases such as helium and argon, including its mixtures with propane; and application in microchip environments. By coupling FµTP with gas chromatography/mass spectrometry, we show that the polarity principle of the new discharge design allows it to outperform established ionization sources such as dielectric barrier discharge for soft ionization (DBDI) and low-temperature plasma (LTP) at low concentrations of perfluoroalkanes in terms of sensitivity, ionization efficiency, chemical background, linear dynamic range, and limit of detection by a large margin. In negative ion mode, the limit of detection is improved by more than 3-fold compared with that of DBDI and by 8-fold compared with that of LTP. The protonation capability was evaluated by headspace measurements of diisopropyl methylphosphonate in positive ion mode, showing low fragmentation and high stability in comparison to DBDI and LTP.

18.
Anal Chem ; 90(5): 3537-3542, 2018 03 06.
Artigo em Inglês | MEDLINE | ID: mdl-29461807

RESUMO

Dielectric barrier discharges (DBDs) have been used as soft ionization sources (DBDI) for organic mass spectrometry (DBDI-MS) for approximately ten years. Helium-based DBDI is often used because of its good ionization efficiency, low ignition voltage, and homogeneous plasma conditions. Argon needs much higher ignition voltages than helium when the same discharge geometry is used. A filamentary plasma, which is not suitable for soft ionization, may be produced instead of a homogeneous plasma. This difference results in N2, present in helium and argon as an impurity, being Penning-ionized by helium but not by metastable argon atoms. In this study, a mixture of argon and propane (C3H8) was used as an ignition aid to decrease the ignition and working voltages, because propane can be Penning-ionized by argon metastables. This approach leads to homogeneous argon-based DBDI. Furthermore, operating DBDI in an open environment assumes that many uncharged analyte molecules do not interact with the reactant ions. To overcome this disadvantage, we present a novel approach, where the analyte is introduced in an enclosed system through the discharge capillary itself. This nonambient DBDI-MS arrangement is presented and characterized and could advance the novel connection of DBDI with analytical separation techniques such as gas chromatography (GC) and high-pressure liquid chromatography (HPLC) in the near future.

19.
Rapid Commun Mass Spectrom ; 32(13): 1092-1098, 2018 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-29660193

RESUMO

RATIONALE: The potential of an atmospheric pressure ionization source based on a dielectric barrier discharge in helium for the hyphenation of gas chromatography and mass spectrometry (GC/DBDI-MS) has been demonstrated only recently and for a limited range of compounds. Due to its 'soft' ionization properties and the possibility to choose from a variety of atmospheric pressure ionization MS instruments, GC/DBDI-MS has the potential to be an interesting alternative to 'classic' GC/MS techniques. METHODS: The hyphenation of GC with DBDI-MS at atmospheric pressure is used for the determination of semifluorinated n-alkanes in ski wax samples. RESULTS: Different to perfluorinated n-alkanes, which are typically detected as [M - F + O]- and [M - F]- , semifluorinated n-alkanes can be detected both in positive mode as [M - 3H + nO]+ and [M - H + nO]+ (n = 0, 1, 2, and 3) ions, as well as in negative mode as a fragment ion representing the fluorinated part of the respective semifluorinated n-alkane. The method allowed the sensitive detection of semifluorinated n-alkanes with achievable limits of detection (LODs) in the single digit pg range injected on column. To examine the applicability of the GC/DBDI-MS method, semifluorinated n-alkanes were determined in fluorinated ski waxes. Results were confirmed by complimentary GC/electron ionization MS measurements. CONCLUSIONS: The unique SFA ionization patterns serve for complementary unambiguous identification of semifluorinated n-alkane species in positive mode and screening of contained n-alkanes fluorinated chain lengths in negative mode.

20.
J Neurophysiol ; 118(3): 1762-1774, 2017 09 01.
Artigo em Inglês | MEDLINE | ID: mdl-28659462

RESUMO

Smooth pursuit and motion perception have mainly been investigated with stimuli moving along linear trajectories. Here we studied the quality of pursuit movements to curved motion trajectories in human observers and examined whether the pursuit responses would be sensitive enough to discriminate various degrees of curvature. In a two-interval forced-choice task subjects pursued a Gaussian blob moving along a curved trajectory and then indicated in which interval the curve was flatter. We also measured discrimination thresholds for the same curvatures during fixation. Motion curvature had some specific effects on smooth pursuit properties: trajectories with larger amounts of curvature elicited lower open-loop acceleration, lower pursuit gain, and larger catch-up saccades compared with less curved trajectories. Initially, target motion curvatures were underestimated; however, ∼300 ms after pursuit onset pursuit responses closely matched the actual curved trajectory. We calculated perceptual thresholds for curvature discrimination, which were on the order of 1.5 degrees of visual angle (°) for a 7.9° curvature standard. Oculometric sensitivity to curvature discrimination based on the whole pursuit trajectory was quite similar to perceptual performance. Oculometric thresholds based on smaller time windows were higher. Thus smooth pursuit can quite accurately follow moving targets with curved trajectories, but temporal integration over longer periods is necessary to reach perceptual thresholds for curvature discrimination.NEW & NOTEWORTHY Even though motion trajectories in the real world are frequently curved, most studies of smooth pursuit and motion perception have investigated linear motion. We show that pursuit initially underestimates the curvature of target motion and is able to reproduce the target curvature ∼300 ms after pursuit onset. Temporal integration of target motion over longer periods is necessary for pursuit to reach the level of precision found in perceptual discrimination of curvature.


Assuntos
Discriminação Psicológica , Fixação Ocular , Percepção de Movimento , Acompanhamento Ocular Uniforme , Aceleração , Adulto , Feminino , Humanos , Masculino , Limiar Sensorial
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