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1.
J Neural Eng ; 21(4)2024 Jul 26.
Artigo em Inglês | MEDLINE | ID: mdl-38981500

RESUMO

Objective.To evaluate the inter- and intra-rater reliability for the identification of bad channels among neurologists, EEG Technologists, and naïve research personnel, and to compare their performance with the automated bad channel detection (ABCD) algorithm for detecting bad channels.Approach.Six Neurologists, ten EEG Technologists, and six naïve research personnel (22 raters in total) were asked to rate 1440 real intracranial EEG channels as good or bad. Intra- and interrater kappa statistics were calculated for each group. We then compared each group to the ABCD algorithm which uses spectral and temporal domain features to classify channels as good or bad.Main results.Analysis of channel ratings from our participants revealed variable intra-rater reliability within each group, with no significant differences across groups. Inter-rater reliability was moderate among neurologists and EEG Technologists but minimal among naïve participants. Neurologists demonstrated a slightly higher consistency in ratings than EEG Technologists. Both groups occasionally misclassified flat channels as good, and participants generally focused on low-frequency content for their assessments. The ABCD algorithm, in contrast, relied more on high-frequency content. A logistic regression model showed a linear relationship between the algorithm's ratings and user responses for predominantly good channels, but less so for channels rated as bad. Sensitivity and specificity analyses further highlighted differences in rating patterns among the groups, with neurologists showing higher sensitivity and naïve personnel higher specificity.Significance.Our study reveals the bias in human assessments of intracranial electroencephalography (iEEG) data quality and the tendency of even experienced professionals to overlook certain bad channels, highlighting the need for standardized, unbiased methods. The ABCD algorithm, outperforming human raters, suggests the potential of automated solutions for more reliable iEEG interpretation and seizure characterization, offering a reliable approach free from human biases.


Assuntos
Algoritmos , Humanos , Reprodutibilidade dos Testes , Variações Dependentes do Observador , Eletrocorticografia/métodos , Eletrocorticografia/normas , Eletroencefalografia/métodos , Eletroencefalografia/normas , Neurologistas/estatística & dados numéricos , Neurologistas/normas
2.
bioRxiv ; 2024 Jul 08.
Artigo em Inglês | MEDLINE | ID: mdl-39026817

RESUMO

How do we make good decisions in uncertain environments? In psychology and neuroscience, the classic answer is that we calculate the value of each option and then compare the values to choose the most rewarding, modulo some exploratory noise. An ethologist, conversely, would argue that we commit to one option until its value drops below a threshold, at which point we start exploring other options. In order to determine which view better describes human decision-making, we developed a novel, foraging-inspired sequential decision-making model and used it to ask whether humans compare to threshold ("Forage") or compare alternatives ("Reinforcement-Learn" [RL]). We found that the foraging model was a better fit for participant behavior, better predicted the participants' tendency to repeat choices, and predicted the existence of held-out participants with a pattern of choice that was almost impossible under RL. Together, these results suggest that humans use foraging computations, rather than RL, even in classic reinforcement learning tasks.

3.
bioRxiv ; 2024 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-38895240

RESUMO

Decision-making in uncertain environments often leads to varied outcomes. Understanding how individuals interpret the causes of unexpected feedback is crucial for adaptive behavior and mental well-being. Uncertainty can be broadly categorized into two components: volatility and stochasticity. Volatility is about how quickly conditions change, impacting results. Stochasticity, on the other hand, refers to outcomes affected by random chance or "luck". Understanding these factors enables individuals to have more effective environmental analysis and strategy implementation (explore or exploit) for future decisions. This study investigates how anxiety and apathy, two prevalent affective states, influence the perceptions of uncertainty and exploratory behavior. Participants (N = 1001) completed a restless three-armed bandit task that was analyzed using latent state models. Anxious individuals perceived uncertainty as more volatile, leading to increased exploration and learning rates, especially after reward omission. Conversely, apathetic individuals viewed uncertainty as more stochastic, resulting in decreased exploration and learning rates. The perceived volatility-to-stochasticity ratio mediated the anxiety-exploration relationship post-adverse outcomes. Dimensionality reduction showed exploration and uncertainty estimation to be distinct but related latent factors shaping a manifold of adaptive behavior that is modulated by anxiety and apathy. These findings reveal distinct computational mechanisms for how anxiety and apathy influence decision-making, providing a framework for understanding cognitive and affective processes in neuropsychiatric disorders.

4.
medRxiv ; 2024 May 31.
Artigo em Inglês | MEDLINE | ID: mdl-38853937

RESUMO

Repetitive transcranial magnetic stimulation (rTMS) therapy could be improved by better and earlier prediction of response. Latent class mixture (LCMM) and non-linear mixed effects (NLME) modelling have been applied to model the trajectories of antidepressant response (or non-response) to TMS, but it is not known whether such models can predict clinical outcomes. We compared LCMM and NLME approaches to model the antidepressant response to TMS in a naturalistic sample of 238 patients receiving rTMS for treatment resistant depression (TRD), across multiple coils and protocols. We then compared the predictive power of those models. LCMM trajectories were influenced largely by baseline symptom severity, but baseline symptoms provided little predictive power for later antidepressant response. Rather, the optimal LCMM model was a nonlinear two-class model that accounted for baseline symptoms. This model accurately predicted patient response at 4 weeks of treatment (AUC = 0.70, 95% CI = [0.52-0.87]), but not before. NLME offered slightly improved predictive performance at 4 weeks of treatment (AUC = 0.76, 95% CI = [0.58 - 0.94], but likewise, not before. In showing the predictive validity of these approaches to model response trajectories to rTMS, we provided preliminary evidence that trajectory modeling could be used to guide future treatment decisions.

5.
Neuroimage ; 290: 120557, 2024 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-38423264

RESUMO

BACKGROUND: Time series analysis is critical for understanding brain signals and their relationship to behavior and cognition. Cluster-based permutation tests (CBPT) are commonly used to analyze a variety of electrophysiological signals including EEG, MEG, ECoG, and sEEG data without a priori assumptions about specific temporal effects. However, two major limitations of CBPT include the inability to directly analyze experiments with multiple fixed effects and the inability to account for random effects (e.g. variability across subjects). Here, we propose a flexible multi-step hypothesis testing strategy using CBPT with Linear Mixed Effects Models (LMEs) and Generalized Linear Mixed Effects Models (GLMEs) that can be applied to a wide range of experimental designs and data types. METHODS: We first evaluate the statistical robustness of LMEs and GLMEs using simulated data distributions. Second, we apply a multi-step hypothesis testing strategy to analyze ERPs and broadband power signals extracted from human ECoG recordings collected during a simple image viewing experiment with image category and novelty as fixed effects. Third, we assess the statistical power differences between analyzing signals with CBPT using LMEs compared to CBPT using separate t-tests run on each fixed effect through simulations that emulate broadband power signals. Finally, we apply CBPT using GLMEs to high-gamma burst data to demonstrate the extension of the proposed method to the analysis of nonlinear data. RESULTS: First, we found that LMEs and GLMEs are robust statistical models. In simple simulations LMEs produced highly congruent results with other appropriately applied linear statistical models, but LMEs outperformed many linear statistical models in the analysis of "suboptimal" data and maintained power better than analyzing individual fixed effects with separate t-tests. GLMEs also performed similarly to other nonlinear statistical models. Second, in real world human ECoG data, LMEs performed at least as well as separate t-tests when applied to predefined time windows or when used in conjunction with CBPT. Additionally, fixed effects time courses extracted with CBPT using LMEs from group-level models of pseudo-populations replicated latency effects found in individual category-selective channels. Third, analysis of simulated broadband power signals demonstrated that CBPT using LMEs was superior to CBPT using separate t-tests in identifying time windows with significant fixed effects especially for small effect sizes. Lastly, the analysis of high-gamma burst data using CBPT with GLMEs produced results consistent with CBPT using LMEs applied to broadband power data. CONCLUSIONS: We propose a general approach for statistical analysis of electrophysiological data using CBPT in conjunction with LMEs and GLMEs. We demonstrate that this method is robust for experiments with multiple fixed effects and applicable to the analysis of linear and nonlinear data. Our methodology maximizes the statistical power available in a dataset across multiple experimental variables while accounting for hierarchical random effects and controlling FWER across fixed effects. This approach substantially improves power leading to better reproducibility. Additionally, CBPT using LMEs and GLMEs can be used to analyze individual channels or pseudo-population data for the comparison of functional or anatomical groups of data.


Assuntos
Encéfalo , Projetos de Pesquisa , Humanos , Reprodutibilidade dos Testes , Encéfalo/fisiologia , Modelos Estatísticos , Modelos Lineares
6.
iScience ; 26(11): 108047, 2023 Nov 17.
Artigo em Inglês | MEDLINE | ID: mdl-37867949

RESUMO

The ability to perform motor actions depends, in part, on the brain's initial state. We hypothesized that initial state dependence is a more general principle and applies to cognitive control. To test this idea, we examined human single units recorded from the dorsolateral prefrontal (dlPFC) cortex and dorsal anterior cingulate cortex (dACC) during a task that interleaves motor and perceptual conflict trials, the multisource interference task (MSIT). In both brain regions, variability in pre-trial firing rates predicted subsequent reaction time (RT) on conflict trials. In dlPFC, ensemble firing rate patterns suggested the existence of domain-specific initial states, while in dACC, firing patterns were more consistent with a domain-general initial state. The deployment of shared and independent factors that we observe for conflict resolution may allow for flexible and fast responses mediated by cognitive initial states. These results also support hypotheses that place dACC hierarchically earlier than dlPFC in proactive control.

7.
Artigo em Inglês | MEDLINE | ID: mdl-37808228

RESUMO

Human behavior is incredibly complex and the factors that drive decision making-from instinct, to strategy, to biases between individuals-often vary over multiple timescales. In this paper, we design a predictive framework that learns representations to encode an individual's 'behavioral style', i.e. long-term behavioral trends, while simultaneously predicting future actions and choices. The model explicitly separates representations into three latent spaces: the recent past space, the short-term space, and the long-term space where we hope to capture individual differences. To simultaneously extract both global and local variables from complex human behavior, our method combines a multi-scale temporal convolutional network with latent prediction tasks, where we encourage embeddings across the entire sequence, as well as subsets of the sequence, to be mapped to similar points in the latent space. We develop and apply our method to a large-scale behavioral dataset from 1,000 humans playing a 3-armed bandit task, and analyze what our model's resulting embeddings reveal about the human decision making process. In addition to predicting future choices, we show that our model can learn rich representations of human behavior over multiple timescales and provide signatures of differences in individuals.

8.
bioRxiv ; 2023 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-37425723

RESUMO

Exploration-exploitation decision-making is a feature of daily life that is altered in a number of neuropsychiatric conditions. Humans display a range of exploration and exploitation behaviors, which can be affected by apathy and anxiety. It remains unknown how factors underlying decision-making generate the spectrum of observed exploration-exploitation behavior and how they relate to states of anxiety and apathy. Here, we report a latent structure underlying sequential exploration and exploitation decisions that explains variation in anxiety and apathy. 1001 participants in a gender-balanced sample completed a three-armed restless bandit task along with psychiatric symptom surveys. Using dimensionality reduction methods, we found that decision sequences reduced to a low-dimensional manifold. The axes of this manifold explained individual differences in the balance between states of exploration and exploitation and the stability of those states, as determined by a statistical mechanics model of decision-making. Position along the balance axis was correlated with opposing symptoms of behavioral apathy and anxiety, while position along the stability axis correlated with the level of emotional apathy. This result resolves a paradox over how these symptoms can be correlated in samples but have opposite effects on behavior. Furthermore, this work provides a basis for using behavioral manifolds to reveal relationships between behavioral dynamics and affective states, with important implications for behavioral measurement approaches to neuropsychiatric conditions.

9.
bioRxiv ; 2023 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-37034791

RESUMO

Background: Time series analysis is critical for understanding brain signals and their relationship to behavior and cognition. Cluster-based permutation tests (CBPT) are commonly used to analyze a variety of electrophysiological signals including EEG, MEG, ECoG, and sEEG data without a priori assumptions about specific temporal effects. However, two major limitations of CBPT include the inability to directly analyze experiments with multiple fixed effects and the inability to account for random effects (e.g. variability across subjects). Here, we propose a flexible multi-step hypothesis testing strategy using CBPT with Linear Mixed Effects Models (LMEs) and Generalized Linear Mixed Effects Models (GLMEs) that can be applied to a wide range of experimental designs and data types. Methods: We first evaluate the statistical robustness of LMEs and GLMEs using simulated data distributions. Second, we apply a multi-step hypothesis testing strategy to analyze ERPs and broadband power signals extracted from human ECoG recordings collected during a simple image viewing experiment with image category and novelty as fixed effects. Third, we assess the statistical power differences between analyzing signals with CBPT using LMEs compared to CBPT using separate t-tests run on each fixed effect through simulations that emulate broadband power signals. Finally, we apply CBPT using GLMEs to high-gamma burst data to demonstrate the extension of the proposed method to the analysis of nonlinear data. Results: First, we found that LMEs and GLMEs are robust statistical models. In simple simulations LMEs produced highly congruent results with other appropriately applied linear statistical models, but LMEs outperformed many linear statistical models in the analysis of "suboptimal" data and maintained power better than analyzing individual fixed effects with separate t-tests. GLMEs also performed similarly to other nonlinear statistical models. Second, in real world human ECoG data, LMEs performed at least as well as separate t-tests when applied to predefined time windows or when used in conjunction with CBPT. Additionally, fixed effects time courses extracted with CBPT using LMEs from group-level models of pseudo-populations replicated latency effects found in individual category-selective channels. Third, analysis of simulated broadband power signals demonstrated that CBPT using LMEs was superior to CBPT using separate t-tests in identifying time windows with significant fixed effects especially for small effect sizes. Lastly, the analysis of high-gamma burst data using CBPT with GLMEs produced results consistent with CBPT using LMEs applied to broadband power data. Conclusions: We propose a general approach for statistical analysis of electrophysiological data using CBPT in conjunction with LMEs and GLMEs. We demonstrate that this method is robust for experiments with multiple fixed effects and applicable to the analysis of linear and nonlinear data. Our methodology maximizes the statistical power available in a dataset across multiple experimental variables while accounting for hierarchical random effects and controlling FWER across fixed effects. This approach substantially improves power and accuracy leading to better reproducibility. Additionally, CBPT using LMEs and GLMEs can be used to analyze individual channels or pseudo-population data for the comparison of functional or anatomical groups of data.

10.
Addit Manuf ; 67: 103468, 2023 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-36925558

RESUMO

The onset of the 2019 novel coronavirus disease (COVID-19) led to a shortage of personal protective equipment (PPE), medical devices, and other medical supplies causing many stakeholders and the general public alike to turn to additive manufacturing (AM) as a stopgap when normally accessible devices were not available. However, without a method to test these AM constructs, there continued to be a disconnect between AM suppliers and the community's needs. The objective of this study was to characterize the pressure drop and leakage of four different publicly available AM face mask models with two filter material combinations, as well as to investigate the impact of frame modification techniques including the use of foam strips and hot-water face forming to improve fit when the masks are donned on manikin head forms. AM face mask frame designs were downloaded from public repositories during the early stages of the COVID-19 pandemic. AM face masks were fabricated and tested on manikin head forms within a custom chamber containing dry aerosolized NaCl. Pressure drops, particle penetration, and leakage were evaluated for various flow rates and NaCl concentrations. Results indicated that filter material combination and frame modification played a major role in the overall performance of the AM face masks studied. Filter material combinations showed improved performance when high filtration fabric was used, and the cross-sectional area of the fabric was increased. AM frame modifications appeared to improve AM face mask leakage performance by as much as 69.6%.

11.
Artigo em Inglês | MEDLINE | ID: mdl-36894434

RESUMO

BACKGROUND: Stress is a major risk factor for depression, and both are associated with important changes in decision-making patterns. However, decades of research have only weakly connected physiological measurements of stress to the subjective experience of depression. Here, we examined the relationship between prolonged physiological stress, mood, and explore-exploit decision making in a population navigating a dynamic environment under stress: health care workers during the COVID-19 pandemic. METHODS: We measured hair cortisol levels in health care workers who completed symptom surveys and performed an explore-exploit restless-bandit decision-making task; 32 participants were included in the final analysis. Hidden Markov and reinforcement learning models assessed task behavior. RESULTS: Participants with higher hair cortisol exhibited less exploration (r = -0.36, p = .046). Higher cortisol levels predicted less learning during exploration (ß = -0.42, false discovery rate [FDR]-corrected p [pFDR] = .022). Importantly, mood did not independently correlate with cortisol concentration, but rather explained additional variance (ß = 0.46, pFDR = .022) and strengthened the relationship between higher cortisol and lower levels of exploratory learning (ß = -0.47, pFDR = .022) in a joint model. These results were corroborated by a reinforcement learning model, which revealed less learning with higher hair cortisol and low mood (ß = -0.67, pFDR = .002). CONCLUSIONS: These results imply that prolonged physiological stress may limit learning from new information and lead to cognitive rigidity, potentially contributing to burnout. Decision-making measures link subjective mood states to measured physiological stress, suggesting that they should be incorporated into future biomarker studies of mood and stress conditions.


Assuntos
COVID-19 , Depressão , Humanos , Depressão/psicologia , Estresse Psicológico , Hidrocortisona/análise , Pandemias , Estresse Fisiológico
12.
ArXiv ; 2023 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-36866229

RESUMO

Human behavior is incredibly complex and the factors that drive decision making--from instinct, to strategy, to biases between individuals--often vary over multiple timescales. In this paper, we design a predictive framework that learns representations to encode an individual's 'behavioral style', i.e. long-term behavioral trends, while simultaneously predicting future actions and choices. The model explicitly separates representations into three latent spaces: the recent past space, the short-term space, and the long-term space where we hope to capture individual differences. To simultaneously extract both global and local variables from complex human behavior, our method combines a multi-scale temporal convolutional network with latent prediction tasks, where we encourage embeddings across the entire sequence, as well as subsets of the sequence, to be mapped to similar points in the latent space. We develop and apply our method to a large-scale behavioral dataset from 1,000 humans playing a 3-armed bandit task, and analyze what our model's resulting embeddings reveal about the human decision making process. In addition to predicting future choices, we show that our model can learn rich representations of human behavior over multiple timescales and provide signatures of differences in individuals.

14.
Front Pain Res (Lausanne) ; 4: 1072786, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36937564

RESUMO

Objectives: This article presents a method-including hardware configuration, sampling rate, filtering settings, and other data analysis techniques-to measure evoked compound action potentials (ECAPs) during spinal cord stimulation (SCS) in humans with externalized percutaneous electrodes. The goal is to provide a robust and standardized protocol for measuring ECAPs on the non-stimulation contacts and to demonstrate how measured signals depend on hardware and processing decisions. Methods: Two participants were implanted with percutaneous leads for the treatment of chronic pain with externalized leads during a trial period for stimulation and recording. The leads were connected to a Neuralynx ATLAS system allowing us to simultaneously stimulate and record through selected electrodes. We examined different hardware settings, such as online filters and sampling rate, as well as processing techniques, such as stimulation artifact removal and offline filters, and measured the effects on the ECAPs metrics: the first negative peak (N1) time and peak-valley amplitude. Results: For accurate measurements of ECAPs, the hardware sampling rate should be least at 8 kHz and should use a high pass filter with a low cutoff frequency, such as 0.1 Hz, to eliminate baseline drift and saturation (railing). Stimulation artifact removal can use a double exponential or a second-order polynomial. The polynomial fit is 6.4 times faster on average in computation time than the double exponential, while the resulting ECAPs' N1 time and peak-valley amplitude are similar between the two. If the baseline raw measurement drifts with stimulation, a median filter with a 100-ms window or a high pass filter with an 80-Hz cutoff frequency preserves the ECAPs. Conclusions: This work is the first comprehensive analysis of hardware and processing variations on the observed ECAPs from SCS leads. It sets recommendations to properly record and process ECAPs from the non-stimulation contacts on the implantable leads.

15.
Sci Rep ; 13(1): 5104, 2023 03 29.
Artigo em Inglês | MEDLINE | ID: mdl-36991010

RESUMO

Tissue containment systems (TCS) are medical devices that may be used during morcellation procedures during minimally invasive laparoscopic surgery. TCS are not new devices but their use as a potential mitigation for the spread of occult malignancy during laparoscopic power morcellation of fibroids and/or the uterus has been the subject of interest following reports of upstaging of previously undetected sarcoma in women who underwent a laparoscopic hysterectomy. Development of standardized test methods and acceptance criteria to evaluate the safety and performance of these devices will speed development, allowing for more devices to benefit patients. As a part of this study, a series of preclinical experimental bench test methods were developed to evaluate the mechanical and leakage performance of TCS that may be used in power morcellation procedures. Experimental tests were developed to evaluate mechanical integrity, e.g., tensile, burst, puncture, and penetration strengths for the TCS, and leakage integrity, e.g., dye and microbiological leakage (both acting as surrogates for blood and cancer cells) through the TCS. In addition, to evaluate both mechanical integrity and leakage integrity as a combined methodology, partial puncture and dye leakage was conducted on the TCS to evaluate the potential for leakage due to partial damage caused by surgical tools. Samples from 7 different TCSs were subjected to preclinical bench testing to evaluate leakage and mechanical performance. The performance of the TCSs varied significantly between different brands. The leakage pressure of the TCS varied between 26 and > 1293 mmHg for the 7 TCS brands. Similarly, the tensile force to failure, burst pressure, and puncture force varied between 14 and 80 MPa, 2 and 78 psi, and 2.5 N and 47 N, respectively. The mechanical failure and leakage performance of the TCS were different for homogeneous and composite TCSs. The test methods reported in this study may facilitate the development and regulatory review of these devices, may help compare TCS performance between devices, and increase provider and patient accessibility to improved tissue containment technologies.


Assuntos
Laparoscopia , Leiomioma , Miomectomia Uterina , Neoplasias Uterinas , Humanos , Feminino , Neoplasias Uterinas/patologia , Miomectomia Uterina/métodos , Leiomioma/patologia , Útero/patologia , Histerectomia/métodos , Laparoscopia/métodos
16.
Epilepsia ; 64(1): 6-16, 2023 01.
Artigo em Inglês | MEDLINE | ID: mdl-36300659

RESUMO

Visual review of intracranial electroencephalography (iEEG) is often an essential component for defining the zone of resection for epilepsy surgery. Unsupervised approaches using machine and deep learning are being employed to identify seizure onset zones (SOZs). This prompts a more comprehensive understanding of the reliability of visual review as a reference standard. We sought to summarize existing evidence on the reliability of visual review of iEEG in defining the SOZ for patients undergoing surgical workup and understand its implications for algorithm accuracy for SOZ prediction. We performed a systematic literature review on the reliability of determining the SOZ by visual inspection of iEEG in accordance with best practices. Searches included MEDLINE, Embase, Cochrane Library, and Web of Science on May 8, 2022. We included studies with a quantitative reliability assessment within or between observers. Risk of bias assessment was performed with QUADAS-2. A model was developed to estimate the effect of Cohen kappa on the maximum possible accuracy for any algorithm detecting the SOZ. Two thousand three hundred thirty-eight articles were identified and evaluated, of which one met inclusion criteria. This study assessed reliability between two reviewers for 10 patients with temporal lobe epilepsy and found a kappa of .80. These limited data were used to model the maximum accuracy of automated methods. For a hypothetical algorithm that is 100% accurate to the ground truth, the maximum accuracy modeled with a Cohen kappa of .8 ranged from .60 to .85 (F-2). The reliability of reviewing iEEG to localize the SOZ has been evaluated only in a small sample of patients with methodologic limitations. The ability of any algorithm to estimate the SOZ is notably limited by the reliability of iEEG interpretation. We acknowledge practical limitations of rigorous reliability analysis, and we propose design characteristics and study questions to further investigate reliability.


Assuntos
Epilepsia do Lobo Temporal , Convulsões , Humanos , Convulsões/diagnóstico , Convulsões/cirurgia , Reprodutibilidade dos Testes , Eletroencefalografia/métodos , Epilepsia do Lobo Temporal/cirurgia , Eletrocorticografia/métodos
17.
J Am Chem Soc ; 144(24): 11003-11009, 2022 Jun 22.
Artigo em Inglês | MEDLINE | ID: mdl-35695094

RESUMO

The organometallic on-surface synthesis of the eight-membered sp2 carbon-based ring cyclooctatetraene (C8H8, Cot) with the neighboring rare-earth elements ytterbium and thulium yields fundamentally different products for the two lanthanides, when conducted on graphene (Gr) close to the charge neutrality point. Sandwich-molecular YbCot wires of more than 500 Å length being composed of an alternating sequence of Yb atoms and upright-standing Cot molecules result from the on-surface synthesis with Yb. In contrast, repulsively interacting TmCot dots consisting of a single Cot molecule and a single Tm atom result from the on-surface synthesis with Tm. While the YbCot wires are bound through van der Waals interactions to the substrate, the dots are chemisorbed to Gr via the Tm atoms being more electropositive compared to Yb atoms. When the electron chemical potential in Gr is substantially raised (n-doping) through backside doping from an intercalation layer, the reaction product in the synthesis with Tm can be tuned to TmCot sandwich-molecular wires rather than TmCot dots. By use of density functional theory, it is found that the reduced electronegativity of Gr upon n-doping weakens the binding as well as the charge transfer between the reaction intermediate TmCot dot and Gr. Thus, the assembly of the TmCot dots to long TmCot sandwich-molecular wires becomes energetically favorable. It is thereby demonstrated that the electron chemical potential in Gr can be used as a control parameter in an organometallic on-surface synthesis to tune the outcome of a reaction.

18.
Nanoscale ; 14(20): 7682-7691, 2022 May 26.
Artigo em Inglês | MEDLINE | ID: mdl-35546135

RESUMO

From macroscopic heavy-duty permanent magnets to nanodevices, the precise control of the magnetic properties in rare-earth metals is crucial for many applications used in our daily life. Therefore, a detailed understanding and manipulation of the 4f-metals' magnetic properties are key to further boosting the functionalization and efficiency of future applications. We present a proof-of-concept approach consisting of a dysprosium-iridium surface alloy in which graphene adsorption allows us to tailor its magnetic properties. By adsorbing graphene onto a long-range ordered two-dimensional dysprosium-iridium surface alloy, the magnetic 4f-metal atoms are selectively lifted from the surface alloy. This selective skyhook effect introduces a giant magnetic anisotropy in dysprosium atoms as a result of manipulating its geometrical structure within the surface alloy. Introducing and proving this concept by our combined theoretical and experimental approach provides an easy and unambiguous understanding of its underlying mechanism. Our study sets the ground for an alternative path on how to modify the crystal field around 4f-atoms and therefore their magnetic anisotropies.

19.
Nutr Clin Pract ; 37(4): 752-761, 2022 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-35165940

RESUMO

Misconnections between enteral devices and other medical devices have been associated with patient death and serious injuries. To minimize such misconnections, the design of connectors on enteral devices has been standardized. The most common adaptation of the standardized enteral connector is called ENFit. Gastrostomy tubes (G-tubes), which may or may not possess the ENFit connector, are increasingly used to deliver commercial and blenderized diets in home settings to enteral device users. To investigate and compare the performance of G-tubes with and without ENFit connectors, research investigations have recently been performed. However, synthesis of such investigations and quantitative discussion of the consequences of transitioning to ENFit-based G-tube devices has not yet occurred. Here we review the research findings from these studies, with data on patient practices from a Mayo Clinic survey, to estimate the impact on tube feeders in home settings of transitioning to ENFit-based G-tube devices. Extrapolating the findings from these studies to US enteral G-tube patients, 1.5%-8.6% of adult patients and 0.2%-1.9% of pediatric patients may experience perceptible slowing in their gravity feeds if using ENFit-based G-tube devices. About 2.5%-8.6% of adult patients and 0.5%-5.5% of pediatric patients (or their caregivers) may need to push with perceptibly more force for syringe push-based feeding using ENFit-based G-tube devices. Lastly, the article offers suggestions for patients and device manufacturers. [Correction added on 2 May 2022, after first online publication: In the preceding sentence, the percentage of adult patients was revised from 2.5%-8.6% to 1.5%-8.6%.].


Assuntos
Nutrição Enteral , Gastrostomia , Criança , Alimentos Formulados , Humanos , Intubação Gastrointestinal , Seringas
20.
Angew Chem Int Ed Engl ; 61(12): e202115892, 2022 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-35032345

RESUMO

The Co-based complex [Co(H2 B(pz)(pypz))2 ] (py=pyridine, pz=pyrazole) deposited on Ag(111) was investigated with scanning tunneling microscopy at ≈5 K. Due to a bis(tridentate) coordination sphere the molecules aggregate mainly into tetramers. Individual complexes in these tetramers undergo reversible transitions between two states with characteristic image contrasts when current is passed through them or one of their neighbors. Two molecules exhibit this bistability while the other two molecules are stable. The transition rates vary linearly with the tunneling current and exhibit an intriguing dependence on the bias voltage and its polarity. We interpret the states as being due to S=1 /2 and 3 /2 spin states of the Co2+ complex. The image contrast and the orders-of-magnitude variations of the switching yields can be tentatively understood from the calculated orbital structures of the two spin states, thus providing first insights into the mechanism of electron-induced excited spin-state trapping (ELIESST).

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