RESUMO
The bis(iminoxolene)iridium complex (Diso)2IrCl (Diso = N-(2,6-diisopropylphenyl)-4,6-di-tert-butyl-2-imino-o-benzoquinone) reacts with pyridine to give trans-(Diso)2Ir(py)Cl as the kinetic product, with cis-(Diso)2Ir(py)Cl formed as the exclusive thermodynamic product upon heating. Electronic spectra and density functional theory calculations point to very similar electronic structures for the cis and trans isomers, with a nonbonding iminoxolene-centered HOMO and a metal-iminoxolene π* LUMO. The triplet states of cis-(Diso)2Ir(py)Cl and cis-[(Diso)2Ir(py)2]+ (but not trans-(Diso)2Ir(py)Cl) are unusually low in energy (1000-1500 cm-1 above the singlets), as shown by variable-temperature NMR spectroscopy. The low-energy triplets are attributed to a change in dihedral angle in the iminoxolenes, which allows a partial π interaction that cannot be achieved in the trans octahedral compounds. Mechanistic studies of the trans-cis isomerization in toluene indicate that the reaction proceeds via isomerization of the five-coordinate species to a form with cis iminoxolene ligands and an apical oxygen. This form is high in energy due to the loss of a secondary iminoxolene-to-iridium π-donor interaction that is possible in the trans form but not in the cis form for the square pyramidal structures. This stereoelectronic effect, combined with the poorer binding of pyridine in trans-(Diso)2Ir(py)Cl due to the interactions of the N-aryl substituents with the pyridine, makes the pyridine dissociate faster from the trans isomer by a factor of 108 at room temperature.
RESUMO
N-(2,6-Diisopropylphenyl)-4,6-di-tert-butyl-o-iminobenzoquinone (Diso) reacts with the (cyclooctadiene)iridium chloride dimer to form a monoiminoxolene complex, (Diso)Ir(cod)Cl. Reaction of 2 equiv of the iminoquinone with chlorobis(cyclooctene)iridium dimer affords the bis-iminoxolene (Diso)2IrCl. This five-coordinate complex adopts a distorted square pyramidal structure with an apical chloride ligand and undergoes halide exchange to form an air-stable iodide complex. (Diso)2IrCl can be reduced by one electron to form neutral, square planar (Diso)2Ir, while oxidation with PhICl2 gives octahedral trans-(Diso)2IrCl2. The cis isomer can be prepared by air oxidation of (Diso)2IrCl; cis/trans isomerization is not observed even on prolonged heating. Structural and spectroscopic features of the complexes are consistent with the presence of strong, covalent π bonding between the metal and the iminoxolene ligands, with structural data suggesting between 45 and 60% iridium character in the π bonding orbitals, depending on the ancillary ligands. The spectroscopic similarity of (Diso)2Ir and (Diso)2IrCl to their cobalt congeners suggests that the first-row metal complexes likewise have appreciably covalent metal-iminoxolene π bonds.
RESUMO
The design of effective electrocatalysts for carbon dioxide reduction requires understanding the mechanistic underpinnings governing the binding, reduction, and protonation of CO2. A critical aspect to understanding and tuning these factors for optimal catalysis revolves around controlling the electronic environments of the primary and secondary coordination sphere. Herein we report a series of para-substituted cobalt aminopyridine macrocyclic catalysts 2-4 capable of carrying out the electrochemical reduction of CO2 to CO. Under catalytic conditions, complexes 2-4, as well as the unsubstituted cobalt aminopyridine complex 1, exhibit icat/ip values ranging from 144 to 781. Complexes 2 and 4 exhibit a pronounced precatalytic wave suggestive of an ECEC mechanism. A Hammett analysis reveals that ligand modifications with electron-donating groups enhance catalysis (ρ < 0), indicative of positive charge buildup in the transition state. This trend also extends to the CoI/0 potential, where complexes possessing more negative E(CoI/0) reductions exhibit greater icat/ip values. The reported modifications offer a synthetic lever to tune catalytic activity, orthogonal to our previous study of the role of pendant hydrogen bond donors.
RESUMO
We report here the efficient reduction of CO2 to CO by cobalt aminopyridine macrocycles. The effect of the pendant amines on catalysis was investigated. Several cobalt complexes based on the azacalix[4](2,6)pyridine framework with different substitutions on the pendant amine groups have been synthesized (R = H (1), Me (2), and allyl (3)), and their electrocatalytic properties were explored. Under an atmosphere of CO2 and in the presence of weak Brønsted acids, large catalytic currents are observed for 1, corresponding to the reduction of CO2 to CO with excellent Faradaic efficiency (98 ± 2%). In comparison, complexes 2 and 3 generate CO with TONs at least 300 times lower than 1, suggesting that the presence of the pendant NH moiety of the secondary amine is crucial for catalysis. Moreover, the presence of NH groups leads to a positive shift in the reduction potential of the Co(I/0) couple, therefore decreasing the overpotential for CO2 reduction.
RESUMO
Anticipating human decisions while performing complex tasks remains a formidable challenge. This study proposes a multimodal machine-learning approach that leverages image features and electroencephalography (EEG) data to predict human response correctness in a demanding visual searching task. Notably, we extract a novel set of image features pertaining to object relationships using the Segment Anything Model (SAM), which enhances prediction accuracy compared to traditional features. Additionally, our approach effectively utilizes a combination of EEG signals and image features to streamline the feature set required for the Random Forest Classifier (RFC) while maintaining high accuracy. The findings of this research hold substantial potential for developing advanced fault alert systems, particularly in critical decision-making environments such as the medical and defence sectors.
Assuntos
Tomada de Decisões , Eletroencefalografia , Aprendizado de Máquina , Humanos , Masculino , Feminino , Adulto , Adulto Jovem , AlgoritmosRESUMO
Object recognition is a complex cognitive process in which information is integrated and processed by various brain regions. Previous studies have shown that both the visual and temporal cortices are active during object recognition and identification. However, although object recognition and object identification are similar, these processes are considered distinct functions in the brain. Despite this, the differentiation between object recognition and identification has yet to be clearly defined for use in brain-computer interface (BCI) applications. This research aims to utilize neural features related to object recognition and identification and classify these features to differentiate between the two processes. The results demonstrate that several classifiers achieved high levels of accuracy, with the XGBoost classifier using a Linear Booster achieving the highest accuracy at 96% and a F1 score of 0.97. This ability to distinguish between object recognition and identification can be a beneficial aspect of a BCI object recognition system as it could help determine the intended target object for a user.
Assuntos
Interfaces Cérebro-Computador , Eletroencefalografia , Encéfalo , Percepção VisualRESUMO
Object recognition and object identification are multifaceted cognitive operations that require various brain regions to synthesize and process information. Prior research has evidenced the activity of both visual and temporal cortices during these tasks. Notwithstanding their similarities, object recognition and identification are recognized as separate brain functions. Drawing from the two-stream hypothesis, our investigation aims to understand whether the channels within the ventral and dorsal streams contain pertinent information for effective model learning regarding object recognition and identification tasks. By utilizing the data we collected during the object recognition and identification experiment, we scrutinized EEGNet models, trained using channels that replicate the two-stream hypothesis pathways, against a model trained using all available channels. The outcomes reveal that the model trained solely using the temporal region delivered a high accuracy level in classifying four distinct object categories. Specifically, the object recognition and object identification models achieved an accuracy of 89% and 85%, respectively. By incorporating the channels that mimic the ventral stream, the model's accuracy was further improved, with the object recognition model and object identification model achieving an accuracy of 95% and 94%, respectively. Furthermore, the Grad-CAM result of the trained models revealed a significant contribution from the ventral and dorsal stream channels toward the training of the EEGNet model. The aim of our study is to pinpoint the optimal channel configuration that provides a swift and accurate brain-computer interface system for object recognition and identification.
Assuntos
Reconhecimento Visual de Modelos , Percepção Visual , Humanos , Encéfalo , Lobo Temporal , Imageamento por Ressonância Magnética , Eletroencefalografia , Mapeamento EncefálicoRESUMO
Detecting concealed objects presents a significant challenge for human and artificial intelligent systems. Detecting concealed objects task necessitates a high level of human attention and cognitive effort to complete the task successfully. Thus, in this study, we use concealed objects as stimuli for our decision-making experimental paradigms to quantify participants' decision-making performance. We applied a deep learning model, Bi-directional Long Short Term Memory (BiLSTM), to predict the participant's decision accuracy by using their electroencephalogram (EEG) signals as input. The classifier model demonstrated high accuracy, reaching 96.1% with an epoching time range of 500 ms following the stimulus event onset. The results revealed that the parietal-occipital brain region provides highly informative information for the classifier in the concealed visual searching tasks. Furthermore, the neural mechanism underlying the concealed visual-searching and decision-making process was explained by analyzing serial EEG components. The findings of this study could contribute to the development of a fault alert system, which has the potential to improve human decision-making performance.
Assuntos
Encéfalo , Eletroencefalografia , Humanos , Inteligência Artificial , Mapeamento Encefálico , AtençãoRESUMO
Situational awareness (SA) is vital for understanding our surroundings. Multiple variables, including inattentive blindness (IB), contribute to the deterioration of SA, which may have detrimental effects on individuals' cognitive performance. IB occurs due to attentional limitations, ignoring critical information and resulting in a loss of SA and a decline in general performance, particularly in complicated situations requiring substantial cognitive resources. To the best of our knowledge, however, past research has not fully uncovered the neurological characteristics of IB nor classified these characteristics in life-alike virtual situations. Therefore, the purpose of this study is to determine whether ERP dynamics in the brain may be utilised as a neural feature to predict the occurrence of IB using machine learning (ML) algorithms. In a virtual reality simulation of an IB experiment, 30 participants' behaviour and Electroencephalography (EEG) measurements were obtained. Participants were given a target detection task in the IB experiment without knowing the unattended shapes displayed on the background building. The targets were presented in three different sensory modalities (auditory, visual, and visual-auditory). On the post-experiment questionnaire, participants who claimed not to have noticed the unattended shapes were assigned to the IB group. Subsequently, the Aware group was formed from individuals who reported seeing the unattended shapes. Using EEGNet to classify IB and Aware groups demonstrated a high classification performance. According to the research, ERP brain dynamics are associated with the awareness of unattended shapes and have the potential to serve as a reliable indication for predicting the visual consciousness of unexpected objects.(p/)(p)Clinical relevance- This research offers a potential brain marker for the mixed-reality and BCI systems that will be used in the future to identify cognitive deterioration, maintain attentional capacity, and prevent disasters.
Assuntos
Atenção , Encéfalo , Humanos , Cognição , Potenciais Evocados , CegueiraRESUMO
Reaction of the 9,9-dimethylxanthene-bis(imine)-bis(catechol) ligand XbicH4 with half an equivalent of Zr(acac)4 affords the neutral tetracatecholate complex (XbicH2)2Zr, containing four iminium ions hydrogen bonded to the catecholates. The heteroleptic bis(catecholate)-tetraphenylporphyrin complex (TPP)Zr(XbicH2) is formed from reaction of (TPP)Zr(OAc)2 with XbicH4 in the presence of base. Both compounds adopt an eight-coordinate square antiprismatic geometry around the zirconium center. NMR spectra of (TPP)Zr(XbicH2) show that it is fluxional at room temperature, with homoleptic (XbicH2)2Zr showing fluxionality at higher temperatures. Calculations and kinetic isotope effect measurements suggest that the motions involve dissociation of a single catecholate oxygen and subsequent twisting of the seven-coordinate species. The compounds show reversible one-electron oxidations of each of the bound catecholates to bound semiquinones.
RESUMO
A 15-year-old presented in cardiogenic shock secondary to viral myocarditis requiring venoarterial extracorporeal membrane oxygenation (ECMO) support. He developed large thrombi of the left ventricle and aortic root. Anticoagulation was increased, and medications were initiated to decrease the likelihood of aortic valve opening. He underwent balloon atrial septostomy followed by placement of a left atrial vent. A pigtail catheter was placed in the ascending aorta for direct heparin infusion. Serial echocardiograms showed progressive resolution of the thrombi. He was successfully weaned from ECMO and discharged home without neurological deficits.
Assuntos
Procedimentos Cirúrgicos Cardíacos/métodos , Gerenciamento Clínico , Oxigenação por Membrana Extracorpórea/métodos , Trombose/terapia , Adolescente , Ecocardiografia , Átrios do Coração , Ventrículos do Coração , Humanos , Masculino , Guias de Prática Clínica como AssuntoRESUMO
Plastic bronchitis is an uncommon condition characterized by the production of large pale bronchial casts that obstruct the tracheobronchial tree. The cellular content, cohesiveness, and often rubber-like consistency distinguish bronchial casts from the usual mucus plugs found with such disease states as asthma. Plastic bronchitis can be found secondary to many conditions, and a simplified classification scheme organizes it into two groups: an inflammatory type consisting of casts with an eosinophilic inflammatory infiltrate and an acellular type with a predominance of fibrin distinguished by its relative lack of cellular infiltrate, its mucin predominance, and its appearance only in children with congenital cyanotic heart disease. This report describes a 5-year-old girl who experienced plastic bronchitis 3 months after a Fontan procedure for hypoplastic left heart syndrome that was treated successfully with aerosolized tissue plasminogen activator.
Assuntos
Bronquite/tratamento farmacológico , Fibrinolíticos/administração & dosagem , Técnica de Fontan/métodos , Síndrome do Coração Esquerdo Hipoplásico/cirurgia , Ativador de Plasminogênio Tecidual/administração & dosagem , Administração por Inalação , Bronquite/diagnóstico , Bronquite/etiologia , Broncoscopia , Pré-Escolar , Diagnóstico Diferencial , Feminino , Humanos , Síndrome do Coração Esquerdo Hipoplásico/complicações , Síndrome do Coração Esquerdo Hipoplásico/diagnóstico , Radiografia TorácicaRESUMO
Schiff base condensation of 4,5-diamino-9,9-dimethylxanthene with 4,6-di-tert-butylcatechol-3-carboxaldehyde affords the bis(catecholimine) ligand XbicH4, which can bind metals in both a square bis(catecholate) upper pocket and a pentagonal N2O3 lower pocket. Metalation with PhSiCl3 results in [(XbicH2)SiPh][HCl2], where the silicon adopts a five-coordinate, square pyramidal geometry in the upper pocket and the lower pocket binds to two protons on the imine nitrogens. Deprotonation of the imines with LiOtBu, NaN[SiMe3]2, or AgOAc results in binding of the univalent metal ion in the lower pocket, where it adopts an unusual pentagonal monopyramidal geometry in the solid state. The complexes show irreversible electrochemistry, with oxidations taking place at relatively high potentials.
RESUMO
OBJECTIVE: Neonatal coronary thrombosis is a rarely reported disorder, with variable outcomes described. This study assessed the feasibility and safety of an institutional protocol using tissue plasminogen activator (tPA) administration for the treatment of neonatal coronary artery thrombi. METHODS: They reviewed the outcome of three neonates with clinical evidence of myocardial infarction secondary to coronary thrombosis. All three underwent the tPA treatment protocol. RESULTS: The three described cases presented at 5 hours, 15 hours, and 10 days of life. The patients identified underwent the tPA protocol at least once. There was clinical evidence of improvement in coronary flow, as well as demonstration of increased left ventricular function and decreased mitral regurgitation. No major adverse events occurred. CONCLUSION: Thrombolytic therapy with this tPA protocol may be safe and effective in treating neonates with coronary thrombosis.