Exploring the Early Time Behavior of the Excited States of an Archetype Thermally Activated Delayed Fluorescence Molecule.

Optical pump-probe techniques allow for an in-depth study of dark excited states. Here, we utilize them to map and gain insights into the excited states involved in the thermally activated delayed fluorescence (TADF) mechanism of a benchmark TADF emitter DMAC-TRZ. The results identify different electronic excited states involved in the key TADF transitions and their nature by combining pump-probe and photoluminescence measurements. The photoinduced absorption signals are highly dependent on polarity, affecting the transition oscillator strength but not their relative energy positions. In methylcyclohexane, a strong and vibronically structured local triplet excited state absorption (3LE → 3LEn) is observed, which is quenched in higher polarity solvents as 3CT becomes the lowest triplet state. Furthermore, ultrafast transient absorption (fsTA) confirms the presence of two stable conformers of DMAC-TRZ: (1) quasi-axial (QA) interconverting within 20 ps into (2) quasi-equatorial (QE) in the excited state. Moreover, fsTA highlights how sensitive excited state couplings are to the environment and the molecular conformation.

Covalently linked pyrene antennas for optically dense yet aggregation-resistant light-harvesting systems.

In this study we present a novel energy transfer material inspired by natural light-harvesting antenna arrays, zinc(II) phthalocyanine-pyrene (ZnPcPy). The ZnPcPy system facilitates energy transfer from 16 covalently linked pyrene (Py) donor chromophores to the emissive central zinc(II) phthalocyanine (ZnPc) core. Nearly 98% energy transfer efficiency is determined from the changes in emission decay rates between free MePy to covalently linked Py, supported by comparisons of photoluminescence quantum yields using different excitation wavelengths. A comparative analysis of ZnPcPy and an equivalent mixture of ZnPc and MePy demonstrates the superior light-harvesting performance of the covalently linked system, with energy transfer rates 9705 times higher in the covalently bound system. This covalent strategy allows for very high loadings of absorbing Py chromophores to be achieved while also avoiding exciton quenching that would otherwise arise, with the same strategy widely applicable to other pairs of Forster resonance energy transfer (FRET) chromophores.

A regression model combined convolutional neural network and recurrent neural network for electroencephalogram-based cross-subject fatigue detection.

Fatigue, one of the most important factors affecting road safety, has attracted many researchers' attention. Most existing fatigue detection methods are based on feature engineering and classification models. The feature engineering is greatly influenced by researchers' domain knowledge, which will lead to a poor performance in fatigue detection, especially in cross-subject experiment design. In addition, fatigue detection is often simplified as a classification problem of several discrete states. Models based on deep learning can realize automatic feature extraction without the limitation of researcher's domain knowledge. Therefore, this paper proposes a regression model combined convolutional neural network and recurrent neural network for electroencephalogram-based (EEG-based) cross-subject fatigue detection. At the same time, a twofold random-offset zero-overlapping sampling method is proposed to train a bigger model and reduce overfitting. Compared with existing results, the proposed method achieves a much better result of 0.94 correlation coefficient (COR) and 0.09 root mean square error (RMSE) in a within-subject experiment design. What is more, there is no misclassification between awake and drowsy states. For cross-subject experiment design, the COR and RMSE are 0.79 and 0.15, respectively, which are close to the existing within-subject results and better than similar cross-subject results. The cross-subject regression model is very important for fatigue detection application since the fatigue indication is more precise than several discrete states and no model calibration is required for a new user. The twofold random-offset zero-overlapping sampling method can also be used as a reference by other EEG-based deep learning research.

Dissipation, Processing Factors and Dietary Exposure Assessment of Myclobutanil in Tomato.

Myclobutanil residue poses a potential threat to consumers' health. This work aims to investigate the degradation behavior, residue levels, processing factors (PFs) and dietary risk of myclobutanil in tomato. Myclobutanil was analyzed using a modified quick, easy, cheap, effective, rugged, safe (QuEChERS) method combined with ultra-performance liquid chromatography-mass spectrometry (UPLC-MS/MS), and average recoveries ranged from 82% to 102% with relative standard deviations RSDs ≤ 9.1%. After spraying myclobutanil miscible oil under field conditions, the initial concentration of myclobutanil was 0.055 mg/kg, and its dissipation followed the first-order kinetics equation with a half-life of 2.88 days. Myclobutanil was mainly present in the tomato skin, and its concentration was about four times that in the whole tomato. The initial concentration of myclobutanil in raw tomato was 0.100 mg/kg. After washing, peeling, homogenization, simmering and canning, the residual level of myclobutanil decreased to 0.067 mg/kg, 0.023 mg/kg, 0.013 mg/kg, 0.044 mg/kg and 0.041 mg/kg, respectively. Although the procedure of simmering led to an increase in myclobutanil concentration, the PFs were all less than 1 in the whole process, showing that the processing procedure significantly decreased the residual level of myclobutanil canned tomato paste in comparison with the raw agricultural commodity. Washing, peeling, and homogenization played critical roles in reducing pesticide residues. The residues of myclobutanil during the processing of tomato pose low dietary exposure risks to consumers in China, which were acceptable. However, the acute and chronic risk quotient for children revealed that it was necessary to monitor the dietary exposure of pesticide residues for children closely.

A regression method for EEG-based cross-dataset fatigue detection.

Introduction: Fatigue is dangerous for certain jobs requiring continuous concentration. When faced with new datasets, the existing fatigue detection model needs a large amount of electroencephalogram (EEG) data for training, which is resource-consuming and impractical. Although the cross-dataset fatigue detection model does not need to be retrained, no one has studied this problem previously. Therefore, this study will focus on the design of the cross-dataset fatigue detection model. Methods: This study proposes a regression method for EEG-based cross-dataset fatigue detection. This method is similar to self-supervised learning and can be divided into two steps: pre-training and the domain-specific adaptive step. To extract specific features for different datasets, a pretext task is proposed to distinguish data on different datasets in the pre-training step. Then, in the domain-specific adaptation stage, these specific features are projected into a shared subspace. Moreover, the maximum mean discrepancy (MMD) is exploited to continuously narrow the differences in the subspace so that an inherent connection can be built between datasets. In addition, the attention mechanism is introduced to extract continuous information on spatial features, and the gated recurrent unit (GRU) is used to capture time series information. Results: The accuracy and root mean square error (RMSE) achieved by the proposed method are 59.10% and 0.27, respectively, which significantly outperforms state-of-the-art domain adaptation methods. Discussion: In addition, this study discusses the effect of labeled samples. When the number of labeled samples is 10% of the total number, the accuracy of the proposed model can reach 66.21%. This study fills a vacancy in the field of fatigue detection. In addition, the EEG-based cross-dataset fatigue detection method can be used for reference by other EEG-based deep learning research practices.

Activation of CB1 pathway in the perirhinal cortex is necessary but not sufficient for destabilization of contextual fear memory in rats.

According to the reconsolidation theory, memories can be modified through the destabilization-reconsolidation process. The rodent perirhinal cortex (PER; Brodmann areas 35 and 36) critically participates in the process of fear conditioning. Previous studies showed that some of the parahippocampal regions are critical for contextual fear memory reconsolidation. In our research, through a three-day paradigm of CFC, we showed that protein synthesis in PER of rats is required for memory reconsolidation, and activation of CB1 pathway is necessary but not sufficient in inducing memory destabilization. This result underlines parahippocampal regions in destabilization and reconsolidation process of fear memory besides amygdala and hippocampus.

The Critical Role of nπ* States in the Photophysics and Thermally Activated Delayed Fluorescence of Spiro Acridine-Anthracenone.

The molecular photophysics and thermally activated delayed fluorescence (TADF) in spiro compounds are distinct because of the rigid orthogonal C-C bridging bond between donor and acceptor. The photophysics is found to be highly complex, with unprecedented multiple anti-Kasha emissions from three different singlet states, two of which are one-photon forbidden. The TADF mechanism is critically controlled by local acceptor nπ* states; the singlet nπ* state undergoes rapid intersystem crossing populating an energetically close acceptor ππ* triplet state. The acceptor triplet nπ* state couples nonadiabatically to a CT triplet state mediating reverse intersystem crossing. When the nπ* and CT states are energetically close, TADF is greatly enhanced with rISC rate reaching 107 s-1. We observe neither DF from the singlet nπ* state nor electron transfer (ET) to form the 1CT because there is no ET driving force; however, ET from the higher-energy donor singlet ππ* state readily occurs along with donor emission.

Excited State Dynamics of Thermally Activated Delayed Fluorescence from an Excited State Intramolecular Proton Transfer System.

We describe the photophysical processes that give rise to thermally activated delayed fluorescence in the excited state intramolecular proton transfer (ESIPT) molecule, triquinolonobenzene (TQB). Using transient absorption and time-resolved photoluminescence spectroscopy, we fully characterize prompt and delayed emission, phosphorescence, and oxygen quenching to reveal the reverse intersystem crossing mechanism (rISC). After photoexcitation and rapid ESIPT to the TQB-TB tautomer, emission from S1 is found to compete with thermally activated ISC to an upper triplet state, T2, very close in energy to S1 and limiting photoluminescence quantum yield. T2 slowly decays to the lowest triplet state, T1, via internal conversion. In the presence of oxygen, T2 is quenched to the ground state of the double proton transferred TQB-TC tautomer. Our measurements demonstrate that rISC in TQB occurs from T2 to S1 driven by thermally activated reverse internal conversion from T1 to T2 and support recent calculations by Cao et al. (Cao, Y.; Eng, J.; Penfold, T. J. Excited State Intramolecular Proton Transfer Dynamics for Triplet Harvesting in Organic Molecules. J. Phys. Chem. A 2019, 123, 2640-2649).

Biometric recognition via texture features of eye movement trajectories in a visual searching task.

Biometric recognition technology based on eye-movement dynamics has been in development for more than ten years. Different visual tasks, feature extraction and feature recognition methods are proposed to improve the performance of eye movement biometric system. However, the correct identification and verification rates, especially in long-term experiments, as well as the effects of visual tasks and eye trackers' temporal and spatial resolution are still the foremost considerations in eye movement biometrics. With a focus on these issues, we proposed a new visual searching task for eye movement data collection and a new class of eye movement features for biometric recognition. In order to demonstrate the improvement of this visual searching task being used in eye movement biometrics, three other eye movement feature extraction methods were also tested on our eye movement datasets. Compared with the original results, all three methods yielded better results as expected. In addition, the biometric performance of these four feature extraction methods was also compared using the equal error rate (EER) and Rank-1 identification rate (Rank-1 IR), and the texture features introduced in this paper were ultimately shown to offer some advantages with regard to long-term stability and robustness over time and spatial precision. Finally, the results of different combinations of these methods with a score-level fusion method indicated that multi-biometric methods perform better in most cases.

OsDSSR1, a novel small peptide, enhances drought tolerance in transgenic rice.

Small signaling peptides play important roles in plant development and responses to abiotic and biotic stresses. We have identified a novel small peptide gene in rice, OsDSSR1, which is expressed mainly in the root, stem, node, leaf, and panicle. OsDSSR1 expression is also induced by drought, salinity, ABA, and H2O2 treatment. OsDSSR1 is localized in the nucleus and cytoplasm. Transgenic plants overexpressing OsDSSR1 exhibited enhanced drought stress tolerance and decreased ABA sensitivity as compared to the wild type. Overexpression of OsDSSR1 promoted the accumulation of compatible osmolytes, such as free proline and soluble sugars. OsDSSR1-overexpressing plants displayed enhanced OsSodCc2 and OscAPX expression and superoxide dismutase and ascorbate peroxidase activities under drought stress. RNA-sequencing data revealed that the expression of 72 abiotic stress-responsive genes was significantly altered in homozygous transgenic plants. These stress-responsive candidate genes will aid in expanding our understanding of the mechanisms by which small peptides mediate tolerance in crop species.

The positive effect of venlafaxine on central motor conduction.

OBJECTIVES: Using the triple stimulation technique (TST) and conventional transcranial magnetic stimulation (TMS), this study was designed to investigate the effect of venlafaxine on central motor conduction in healthy adults. PATIENTS AND METHODS: In this crossover, self-controlled trial, eight healthy adult volunteers were randomly divided into groups A and B. In group A, the volunteers were administered 1 venlafaxine capsule once daily for 7 consecutive days, followed by a 3-day break. Next, volunteers in this group received 1 placebo capsule once daily for 7 consecutive days. Group B received the treatments in the opposite order. The index finger tapping test, grip strength test, TST and conventional TMS examination for each hand were recorded before and one week after the administration of venlafaxine or placebo. RESULTS: Compared to the placebo stage, in the venlafaxine stage, the number of index finger taps was significantly increased for both hands, and the TST amplitude and area ratios were significantly increased. The improvement in the TST amplitude ratio was significantly and positively correlated with the improvements in performance on the index finger tapping test. CONCLUSION: Venlafaxine positively regulates central motor conduction in healthy adults.

Lysine Restriction Affects Feed Intake and Amino Acid Metabolism via Gut Microbiome in Piglets.

BACKGROUND/AIMS: Our previous reports suggested that dietary supplementation with lysine influenced intestinal absorption and metabolism of amino acids. In this study, we further investigated the effect of lysine restriction (30%) on feed intake and we also tested the hypothesis that gut microbiome contributed to the potential mechanism of lysine restriction-mediated feeding behavior. Here, we profiled gut microbial communities by sequencing 16S ribosomal ribonucleic acid (rRNA) genes from gut samples as well as growth performance, serum hormones, and intestinal lysine transport in a piglet model. RESULTS: Piglets preferred to the lysine restricted diet when giving three diets and the feed intake was markedly higher in the lysine-restricted group than that in the control group. Altered hormones (leptin, CCK, and ghrelin) might contribute to the feeding behavior caused by lysine restriction. Meanwhile, lysine transporting ability (SLC7A1 and SLC7A2 expression, intestinal electrophysiological changes, and amino acid pool in mesenteric vein) was decreased in response to lysine restriction. Through deep sequencing of bacterial rRNA markers, we observed that bacterial diversity was enhanced in the lysine-restricted group (Shannon H, PD, and Chao1). At the phylum level, lysine restriction enhanced gut Actinobacteria, Saccharibacteria, and Synergistetes abundances. At the family level, Moraxellaceae, Halomonadaceae, Shewanellaceae, Corynebacteriaceae, Bacillaceae, Comamonadaceae, Microbacteriaceae, Caulobacteraceae, and Synergistaceae abundances were increased in response to lysine restriction. Predictive functional profiling of microbial communities by PICRUSt also confirmed that dietary lysine restriction affected gut microbiome, which might further mediate amino acid metabolism, membrane transport, and endocrine system. CONCLUSION: Our results indicated that lysine restriction inhibited intestinal lysine transport and promoted feed intake, which might be associated with gut microbiome.

Mirror-normal difference in the late phase of mental rotation: An ERP study.

Mirror-normal letter discriminations are thought to require mental rotation in order to transform the rotated alphanumeric character into its canonical orientation. Moreover, out-of-plane rotation is likely to occur after in-plane rotation to fully normalize the mirror version before the final mirror-normal judgment. The so-called rotation-related negativity, which varies with orientation, is found in both ERPonset (averaged with respect to stimulus onset) and ERPRT (averaged with respect to response time), representing the involvement of mental rotation in both time windows. Additionally, the mean amplitude of ERPRT correlates with individual performance. We performed a comprehensive analysis of the mirror-normal differences in the early and late phases of mental rotation and deduced that out-of-plane rotation is more likely to occur in the late phase and interacts with both in-plane rotation and the decision-making process, as indicated by both behavioral and electrophysiological findings.

Uncovering the cognitive processes underlying mental rotation: an eye-movement study.

Mental rotation is an important paradigm for spatial ability. Mental-rotation tasks are assumed to involve five or three sequential cognitive-processing states, though this has not been demonstrated experimentally. Here, we investigated how processing states alternate during mental-rotation tasks. Inference was carried out using an advanced statistical modelling and data-driven approach - a discriminative hidden Markov model (dHMM) trained using eye-movement data obtained from an experiment consisting of two different strategies: (I) mentally rotate the right-side figure to be aligned with the left-side figure and (II) mentally rotate the left-side figure to be aligned with the right-side figure. Eye movements were found to contain the necessary information for determining the processing strategy, and the dHMM that best fit our data segmented the mental-rotation process into three hidden states, which we termed encoding and searching, comparison, and searching on one-side pair. Additionally, we applied three classification methods, logistic regression, support vector model and dHMM, of which dHMM predicted the strategies with the highest accuracy (76.8%). Our study did confirm that there are differences in processing states between these two of mental-rotation strategies, and were consistent with the previous suggestion that mental rotation is discrete process that is accomplished in a piecemeal fashion.

A crucial temporal accuracy test of combining EEG and Tobii eye tracker.

Eye tracking and event-related potentials have been widely used in the field of cognitive psychology and neuroscience. Both techniques have the ability to refine cognitive models through a precise timeline description; nevertheless, they also have severe limitations. Combining measures of event-related potentials and eye movements can contribute to cognitive process capture, which provides the possibility to determine precisely when and in which order different cognitive operations occur. Combining of event-related potentials and eye movements has been recently conducted by synchronizing measures from an infrared eye tracker with an electroencephalograph to allow simultaneous data recording. Here, we describe in detail 4 types of co-registration methods for event-related potentials and eye movements on the Tobii platform. Moreover, the present investigation was designed to evaluate the temporal accuracy of data obtained using the 4 methods. We found that the method based on the Tobii Pro Analytics software development kit had a higher degree of temporal accuracy than the other co-registration methods. Furthermore, the reasons for the different temporal accuracies were assessed, and potential measures to correct clock drift were taken. General suggestions are made regarding timing in the co-registration of the electroencephalograph and eye tracker.

Toxicity assessment of hydrogen peroxide on Toll-like receptor system, apoptosis, and mitochondrial respiration in piglets and IPEC-J2 cells.

In this study, expressions of toll-like receptors (TLRs) and apoptosis-related genes in piglets and mitochondrial respiration in intestinal porcine epithelial cells were investigated after hydrogen peroxide (H2O2) exposure. The in vivo results showed that H2O2 influenced intestinal expressions of TLRs and apoptosis related genes. H2O2 treatment (5% and 10%) downregulated uncoupling protein 2 (UCP2) expression in the duodenum (P < 0.05), while low dosage of H2O2 significantly increased UCP2 expression in the jejunum (P < 0.05). In IPEC-J2 cells, H2O2 inhibited cell proliferation (P < 0.05) and caused mitochondrial dysfunction via reducing maximal respiration, spare respiratory, non-mitochondrial respiratory, and ATP production (P < 0.05). However, 50 uM H2O2 significantly enhanced mitochondrial proton leak (P < 0.05). In conclusion, H2O2 affected intestinal TLRs system, apoptosis related genes, and mitochondrial dysfunction in vivo and in vitro models. Meanwhile, low dosage of H2O2 might exhibit a feedback regulatory mechanism against oxidative injury via increasing UCP2 expression and mitochondrial proton leak.

Effects of Lysine deficiency and Lys-Lys dipeptide on cellular apoptosis and amino acids metabolism.

SCOPE: Lysine (Lys) is a common limiting amino acids (AA) for humans and animals and plays an important role in cell proliferation and metabolism, while metabolism of Lys deficiency and its dipeptide is still obscure. Thus, this study mainly investigated the effects of Lys deficiency and Lys-Lys dipeptide on apoptosis and AA metabolism in vitro and in vivo models. METHODS AND RESULTS: Lys deficiency induced cell-cycle arrest and apoptosis and upregulated Lys transporters in vitro and in vivo. SLC7A11, a cystine-glutamate antiporter, was markedly upregulated by Lys deficiency and then further mediated cystine uptake and glutamate release, which was negatively regulated by cystine and glutamate transporters. Meanwhile, Lys deprivation upregulated pept1 expression, which might improve Lys-Lys dipeptide absorption to compensate for the reduced Lys availability. Lys-Lys dipeptide alleviated Lys deficiency induced cell-cycle arrest and apoptosis and influenced AA metabolism. Furthermore, the mammalian target of rapamycin signal might be involved in sensing cellular Lys starvation and Lys-Lys dipeptide. CONCLUSIONS: Altogether, these studies suggest that Lys deficiency impairs AA metabolism and causes apoptosis. Lys-Lys dipeptide serves as a Lys source and alleviates Lys deficiency induced cellular imbalance.

Single-photon sensitive light-in-fight imaging.

The ability to record images with extreme temporal resolution enables a diverse range of applications, such as fluorescence lifetime imaging, time-of-flight depth imaging and characterization of ultrafast processes. Recently, ultrafast imaging schemes have emerged, which require either long acquisition times or raster scanning and have a requirement for sufficient signal that can only be achieved when light is reflected off an object or diffused by a strongly scattering medium. Here we present a demonstration of the potential of single-photon detector arrays for visualization and rapid characterization of events evolving on picosecond time scales. The single-photon sensitivity, temporal resolution and full-field imaging capability enables the observation of light-in-flight in air, as well as the measurement of laser-induced plasma formation and dynamics in its natural environment. The extreme sensitivity and short acquisition times pave the way for real-time imaging of ultrafast processes or visualization and tracking of objects hidden from view.

The effects of venlafaxine on cortical motor area activity in healthy subjects: a pilot study.

In the study, we used functional magnetic resonance imaging associated with behavioral assessment to observe the effects of venlafaxine on the modulation of human motor cortex activation and to provide preliminary data for further assessing its influence on motor functional reorganization after stroke injury. In a randomized, double-blind, crossover study, 8 right-handed subjects received 75 mg of either venlafaxine or a placebo daily over a period of 7 days separated by 3 washout days. The volunteers were asked to execute motor tasks, which included the dynamometer and finger-tapping test. In addition, laboratory tests and functional magnetic resonance imaging examination, before the start of the experiment and after administration of placebo and venlafaxine, were performed. It was shown that the finger-tapping rate of each hand in the venlafaxine stage was significantly improved compared with that observed in the placebo stage (n = 8, F left hand = 57.69, F right hand = 184.48, P < 0.001). The changes in the recorded grip strengths of both hands were not significant between the stages (n = 8, F = 2.63, P > 0.05). In the venlafaxine stage, the activations of the contralateral primary sensorimotor cortex, contralateral premotor cortex, and contralateral supplementary motor area were enhanced significantly, whereas the activation of the bilateral parietal cortices was decreased when compared with the placebo stage. Meanwhile, the enhancement of contralateral primary sensorimotor cortex activation had a positive correlation with the improvement of the finger-tapping rate. It was concluded that venlafaxine could modulate the cortical excitability and improve finger dexterity and reaction speed, which greatly related to the increase of contralateral motor cortical excitability.