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Stress is one of the most pressing problems in society as it severely reduces the physical and mental wellbeing of people. It is therefore of great importance to accurately monitor stress levels, especially in work environments. However, contemporary stress assessments, such as questionnaires and physiological measurements, have practical limitations, mostly related to their subjective or contact-based nature. To assess stress objectively and conveniently, we developed an automated model that detects biomarkers in webcam-recorded facial behavior indicative of heightened stress levels, using computer vision, artificial intelligence, and machine learning techniques. Heart-rate induced skin pulsations and facial muscle activity were extracted from videos of 264 participants that performed an online mental capacity test under considerable time pressure. The model could successfully use these facial biomarkers to explain a significant proportion of individual differences in scores on a self-perceived stress scale. Next, we used the model to objectively score stress levels of 63 military candidates (pre-hiring) and 69 military personnel (post-hiring) that also performed the mental capacity test. Results showed that military personnel expressed facial behavior indicative of significantly higher stress levels than military candidates. This suggests that joining the military heightens overall stress levels. With this study we take the first steps towards a non-contact, automated, and objective measure of stress that is easily applicable in a variety of health and work contexts., Competing Interests: Declaration of competing interest Authors AB and SH declare no competing interests. Author MN declares to have received shares in Neurolytics B.V. in exchange for consultancy on the development of the here reported models in the context of a government funded, joint valorization project in collaboration with Utrecht University., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Organometallic tin-oxo-hydroxo cage compounds offer a promising photoresist platform for extreme ultraviolet photolithography (EUVL). Their reactivity is dominated by the facile breaking of the tin-carbon bonds upon photon or electron irradiation. As the cage is dicationic, it exists as a complex with anions for charge compensation. In the present work, we explore the n -butyltin-oxo cage with two tetrakis(pentafluorophenyl)borate counteranions (TinPFPB). In contrast to the small counterions that are typically used, the bulky PFPB anion absorbs a substantial fraction (∼30%) of the impinging EUV radiation (13.5 nm, 92 eV), and it has its own reactivity upon photoionization. When thin films of the complex are irradiated with EUV radiation at low doses, a positive-tone development is possible, which is rather unique as all other known tin-oxo cage resists show a negative tone (cross-linking) behavior. We propose that the initial positive tone behavior is a result of the chemical modification of the Sn cluster by fragments of the borate anions. For comparison, we include the tetrakis( p -tolyl)borate anion (TB) in the study, which has similar bulkiness, and its complex with the n -butyltin-oxo cage (TinTB) shows the usual negative tone EUV resist behavior. This negative-tone behavior for our control experiment rules out a hypothesis based purely on the steric hindrance of the anion as the cause of the different EUV reactivity.

Obtaining insights into friction at the nanoscopic level and being able to translate these into macroscopic friction behavior in real-world systems is of paramount importance in many contexts, ranging from transportation to high-precision technology and seismology. Since friction is controlled by the local pressure at the contact it is important to be able to detect both the real contact area and the nanoscopic local pressure distribution simultaneously. In this paper, we present a method that uses planarizable molecular probes in combination with fluorescence microscopy to achieve this goal. These probes, inherently twisted in their ground states, undergo planarization under the influence of pressure, leading to bathochromic and hyperchromic shifts of their UV-vis absorption band. This allows us to map the local pressure in mechanical contact from fluorescence by exciting the emission in the long-wavelength region of the absorption band. We demonstrate a linear relationship between fluorescence intensity and (simulated) pressure at the submicron scale. This relationship enables us to experimentally depict the pressure distribution in multiasperity contacts. The method presented here offers a new way of bridging friction studies of the nanoscale model systems and practical situations for which surface roughness plays a crucial role.

With the purpose of identifying a sensitive, robust, and easy-to-measure set of biomarkers to assess stress reactivity, we here study a large set of relatively easy to obtain markers reflecting subjective, autonomic nervous system (ANS), endocrine, and inflammatory responses to acute social stress (n = 101). A subset of the participants was exposed to another social stressor the next day (n = 48) while being measured in the same way. Acute social stress was induced following standardized procedures. The markers investigated were self-reported positive and negative affect, heart rate, electrodermal activity, salivary cortisol, and ten inflammatory markers both in capillary plasma and salivary samples, including IL-22 which has not been studied in response to acute stress in humans before. Robust effects (significant effect in the same direction for both days) were found for self-reported negative affect, heart rate, electrodermal activity, plasma IL-5, plasma IL-22, salivary IL-8 and salivary IL-10. Of these seven markers, the participants' IL-22 responses on the first day were positively correlated to those on the second day. We found no correlations between salivary and capillary plasma stress responses for any of the ten cytokines and somewhat unexpectedly, cytokine responses in saliva seemed more pronounced and more in line with previous literature than cytokines in capillary plasma. In sum, seven robust and easy to obtain biomarkers to measure acute stress response were identified and should be used in future stress research to detect and examine stress reactivity. This includes IL-22 in plasma as a promising novel marker., Competing Interests: The authors report there are no competing interests to declare., (© 2024 The Authors.)

This study examined the extent to which adolescent peer victimization predicted acute inflammatory responses to stress, and whether both resting parasympathetic nervous system (PNS) activity and PNS stress reactivity moderated this association. 83 adolescents (M age = 14.89, SD age = 0.52, 48% female) reported their history of peer victimization and were exposed to a standardized social stress task before and after which dried blood spot samples were collected to assay inflammatory markers. Inflammatory responses to the stress task were assessed with a latent inflammatory change factor using the cytokines interleukin-6 (IL-6), interleukin-10 (IL-10), and tumor necrosis factor-α (TNF-α). PNS functioning, indexed by high-frequency heart rate variability, was measured at rest and during the stressor. Contrary to hypotheses, analyses revealed no direct relation between peer victimization and acute inflammatory responses, and resting PNS activity did not moderate this association. However, peer victimization predicted stronger inflammatory responses among adolescents with weaker PNS reactivity to the stress task (b = 0.63, p = .02). This association was not observed among adolescents with stronger PNS reactivity, for whom a negative but non-significant trend was found. Weaker PNS reactivity may thus indicate victimized adolescents' vulnerability for acute inflammatory responses, whereas stronger PNS reactivity may indicate adolescents' resilience to a social stressor., (© 2023. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

This study addresses concerns about reproducibility in scientific research, focusing on the use of electroencephalography (EEG) and machine learning to estimate mental workload. We established guidelines for reproducible machine learning research using EEG and used these to assess the current state of reproducibility in mental workload modeling. We first started by summarizing the current state of reproducibility efforts in machine learning and in EEG. Next, we performed a systematic literature review on Scopus, Web of Science, ACM Digital Library, and Pubmed databases to find studies about reproducibility in mental workload prediction using EEG. All of this previous work was used to formulate guidelines, which we structured along the widely recognized Cross-Industry Standard Process for Data Mining (CRISP-DM) framework. By using these guidelines, researchers can ensure transparency and comprehensiveness of their methodologies, therewith enhancing collaboration and knowledge-sharing within the scientific community, and enhancing the reliability, usability and significance of EEG and machine learning techniques in general. A second systematic literature review extracted machine learning studies that used EEG to estimate mental workload. We evaluated the reproducibility status of these studies using our guidelines. We highlight areas studied and overlooked and identify current challenges for reproducibility. Our main findings include limitations on reporting performance on unseen test data, open sharing of data and code, and reporting of resources essential for training and inference processes., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2024 Demirezen, Taşkaya Temizel and Brouwer.)

Automatically detecting mental state such as stress from video images of the face could support evaluating stress responses in applicants for high risk jobs or contribute to timely stress detection in challenging operational settings (e.g., aircrew, command center operators). Challenges in automatically estimating mental state include the generalization of models across contexts and across participants. We here aim to create robust models by training them using data from different contexts and including physiological features. Fifty-one participants were exposed to different types of stressors (cognitive, social evaluative and startle) and baseline variants of the stressors. Video, electrocardiogram (ECG), electrodermal activity (EDA) and self-reports (arousal and valence) were recorded. Logistic regression models aimed to classify between high and low arousal and valence across participants, where "high" and "low" were defined relative to the center of the rating scale. Accuracy scores of different models were evaluated: models trained and tested within a specific context (either a baseline or stressor variant of a task), intermediate context (baseline and stressor variant of a task), or general context (all conditions together). Furthermore, for these different model variants, only the video data was included, only the physiological data, or both video and physiological data. We found that all (video, physiological and video-physio) models could successfully distinguish between high- and low-rated arousal and valence, though performance tended to be better for (1) arousal than valence, (2) specific context than intermediate and general contexts, (3) video-physio data than video or physiological data alone. Automatic feature selection resulted in inclusion of 3-20 features, where the models based on video-physio data usually included features from video, ECG and EDA. Still, performance of video-only models approached the performance of video-physio models. Arousal and valence ratings by three experienced human observers scores based on part of the video data did not match with self-reports. In sum, we showed that it is possible to automatically monitor arousal and valence even in relatively general contexts and better than humans can (in the given circumstances), and that non-contact video images of faces capture an important part of the information, which has practical advantages., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest. The author(s) declared that they were an editorial board member of Frontiers, at the time of submission. This had no impact on the peer review process and the final decision., (Copyright © 2024 Bruin, Stuldreher, Perone, Hogenelst, Naber, Kamphuis and Brouwer.)

Extreme ultraviolet lithography has recently been introduced in high-volume production of integrated circuits for manufacturing the smallest features in high-end computer chips. Hybrid organic/inorganic materials are considered as the next generation of photoresists for this technology, but detailed knowledge about the response of such materials to the ionizing radiation used (13.5 nm, 92 eV) is still scarce. In the present work, we use broadband high-harmonic radiation in the energy range 22-70 eV for absorption spectroscopy and photobleaching (that is, the decrease of absorbance) of thin films of an n -butyltin oxo-cage, a representative of the class of metal-based EUV photoresist. The shape of the absorption spectrum in the range 22-92 eV matches well with the spectrum predicted using tabulated atomic cross sections. The photobleaching results are consistent with loss of the butyl side groups due to the breaking of Sn-C bonds following photoionization. Bleaching is strongest in the low-energy range (<40 eV), where the absorption is largely due to the carbon atoms in the organic groups. At higher energies (42-70 eV), absorption is dominated by the tin atoms, and since these remain in the film after photoconversion, the absorption change in this region is smaller. It is estimated that after prolonged irradiation (up to ∼3 J cm -2 in the range 22-40 eV) about 70% of the hydrocarbon groups are removed from the film. The rate of bleaching is high at the beginning of exposure, but it rapidly decreases with increasing conversion. We rationalize this using density functional theory calculations: the first Sn-C bonds are efficiently cleaved (quantum yield Φ ≈ 0.9), because the highest occupied molecular orbitals (HOMOs) (from which an electron is removed after photoionization) are located on Sn-C sigma bonds. In the photoproducts, the HOMO is localized on tin atoms that have lost their hydrocarbon group (formally reduced to the Sn(II) oxidation state), and holes formed on those tin atoms lead to less efficient cleavage reactions. Our results reveal the primary reaction steps following excitation with ionizing radiation of tin-oxo cages. Our methodology represents a systematic approach of studying and quantitatively assessing the performance of new photoresists and as such enables the development of future EUV photoresists., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Contact mechanics, spanning nanometer to tectonic scales, faces long-standing challenges arising from multiscale random roughness, which hinders experimental validation of theories. Understanding multi-asperity rough contacts is vital for addressing catastrophic consequences of these contacts failing such as earthquakes and for diverse technological applications. To visualize such contacts, we introduce a super-resolution microscopy method utilizing spontaneous millisecond ON/OFF fluorescence blinking of contact-sensitive molecular rotor molecules immobilized on a glass coverslip. This technique achieves ∼55 nm lateral imaging resolution for rough poly(methyl methacrylate) and glass spheres on glass contacts. For soft polymer spheres due to large plastic deformation, the resolution improvement does not significantly affect the area of real contact. However, for hard glass spheres, the real contact area is found to be 2.4 times smaller than that found by diffraction-limited imaging. This study highlights, through direct visualization, the impact of material stiffness on the nanoscale structure within the area of real contact.

"Tin-oxo cage" organometallic compounds are considered as photoresists for extreme ultraviolet (EUV) photolithography. To gain insight into their electronic structure and reactivity to ionizing radiation, we trapped bare gas-phase n -butyltin-oxo cage dications [(BuSn) 12 O 14 (OH) 6 ] 2+ in an ion trap and investigated their fragmentation upon soft X-ray photoabsorption by means of mass spectrometry. In complementary experiments, the tin-oxo cages with hydroxide and trifluoroacetate counter-anions were cast in thin films and studied using X-ray transmission spectroscopy. Quantum-chemical calculations were used to interpret the observed spectra. At the carbon K-edge, a distinct pre-edge absorption band can be attributed to transitions in which electrons are promoted from C1s orbitals to the lowest unoccupied molecular orbitals, which are delocalized orbitals with strong antibonding (Sn-C σ*) character. At higher energies, the most prominent resonant transitions involve C-C and C-H σ* valence states and Rydberg (3s and 3p) states. In the solid state, the onset of continuum ionization is shifted by ∼5 eV to lower energy with respect to the gas phase, due to the electrostatic effect of the counterions. The O K-edge also shows a pre-edge absorption, but it is devoid of any specific features, because there are many transitions from the different O1s orbitals to a large number of vacant orbitals. In the gas phase, formation of the parent [(BuSn) 12 O 14 (OH) 6 ] 3+ radical ion is not observed at the C K-edge nor at the O K-edge, because the loss of a butyl group from this species is very efficient. We do observe a number of triply charged photofragment ions, some of which have lost up to 5 butyl groups. Structures of these species are proposed based on quantum-chemical calculations, and pathways of formation are discussed. Our results provide insight into the electronic structure of alkyltin-oxo cages, which is a prerequisite for understanding their response to EUV photons and their performance as EUV photoresists.

Nature's intricate biominerals inspire fundamental questions on self-organization and guide innovations towards functional materials. While advances in synthetic self-organization have enabled many levels of control, generating complex shapes remains difficult. Specifically, controlling morphologies during formation at the single micro/nanostructure level is the key challenge. Here, we steer the self-organization of barium carbonate nanocrystals and amorphous silica into complex nanocomposite morphologies by photogeneration of carbon dioxide (CO 2 ) under ultraviolet (UV) light. Using modulations in the UV light intensity, we select the growth mode of the self-organization process inwards or outwards to form helical and coral-like morphologies respectively. The spatiotemporal control over CO 2 photogeneration allows formation of different morphologies on pre-assigned locations, switching between different growth modes-to form for instance a coral on top of a helix or vice versa , and subtle sculpting and patterning of the nanocomposites during formation. These findings advance the understanding of these versatile self-organization processes and offer new prospects for tailored designs of functional materials using photochemically driven self-organization.

Introduction: Understanding how food neophobia affects food experience may help to shift toward sustainable diets. Previous research suggests that individuals with higher food neophobia are more aroused and attentive when observing food-related stimuli. The present study examined whether electrodermal activity (EDA), as index of arousal, relates to food neophobia outside the lab when exposed to a single piece of food., Methods: The EDA of 153 participants was analyzed as part of a larger experiment conducted at a festival. Participants completed the 10-item Food Neophobia Scale. Subsequently, they saw three lids covering three foods: a hotdog labeled as "meat", a hotdog labeled as "100% plant-based", and tofu labeled as "100% plant-based". Participants lifted the lids consecutively and the area-under-the-curve (AUC) of the skin conductance response (SCR) was captured between 20 s before and 20 s after each food reveal., Results: We found a significant positive correlation between food neophobia and AUC of SCR during presentation of the first and second hotdog and a trend for tofu. These correlations remained significant even when only including the SCR data prior to the food reveal (i.e., an anticipatory response)., Discussion: The association between food neophobia and EDA indicates that food neophobic individuals are more aroused upon the presentation of food. We show for the first time that the anticipation of being presented with food already increased arousal for food neophobic individuals. These findings also indicate that EDA can be meaningfully determined using wearables outside the lab, in a relatively uncontrolled setting for single-trial analysis., Competing Interests: EZ is employee of Unilever Foods Innovation Center Wageningen, Netherlands, a company which markets food products. HH is employed by Kikkoman Europe R&D Laboratory B.V., Netherlands, a company that markets soy sauce, soy sauce-based seasonings and wholesale of oriental foods. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest. The author(s) declared that they were an editorial board member of Frontiers, at the time of submission. This had no impact on the peer review process and the final decision., (Copyright © 2024 Stuldreher, Van der Burg, Velut, Toet, van Os, Hiraguchi, Hogervorst, Zandstra, Van Erp and Brouwer.)

Background: Sleep deprivation (SD) and acute social stress are common, often unavoidable, and frequently co-occurring stressors in high-risk professions. Both stressors are known to acutely induce inflammatory responses and an increasing body of literature suggests this may lead to cognitive impairment. This study examined the combined effects of total SD and acute social stress on cognitive performance and took a comprehensive approach to explore their (shared) underlying mechanism leading to cognitive decline., Method: We recorded cognitive performance on a response inhibition task and a multitask and monitored a range of inflammatory, psychophysiological and self-reported markers in 101 participants, both before and after one night of either sleep (control group: N = 48) or SD (N = 53), and both before and after a social stressor (Trier Social Stress Test)., Results: SD decreased cognitive performance. The social stress test also results in cognitive performance decline in the control group on the response inhibition task, but improved rather than decreased performance of sleep deprived participants on both tasks. The subjective ratings of mental effort also reflect this antagonistic interaction, indicating that the social stressor when sleep-deprived also reduced mental effort. In the inflammatory and physiological measures, this pattern was only reflected by IL-22 in blood. SD reduced blood IL-22 concentrations, and the social stress reduced IL-22 in the control group as well, but not in sleep-deprived participants. There were no interactive effects of SD and social stress on any other inflammatory or psychophysiological measures. The effects of the social stress test on autonomic measures and subjective results suggest that increased arousal may have benefited sleep-deprived participants' cognitive performance., Discussion: SD generally decreased cognitive performance and increased required mental effort. By contrast, the isolated effects of a social stressor were not generic, showing a positive effect on cognitive performance when sleep deprived. Our study is the first that studied combined effects of sleep deprivation and acute social stress on cognitive performance and inflammatory markers. It provides a comprehensive overview of effects of these stressors on a range of variables. We did not show unequivocal evidence of an underlying physiological mechanism explaining changes in performance due to (the combination of) sleep deprivation and social stress, but consider IL-22 as a possible cytokine involved in this mechanism and certainly worth following up on in future research., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2023 The Authors.)

A key challenge in the recycling of multilayer plastic films of polyethylene and polyamide, as typically used for food packaging, is to assess and control the phase separation of the two types of polymers in the recycled material, the specifics of which determine the mechanical strength of the recycled material. However, visualizing the polyamide-in-polyethylene domains with conventional fluorescence methods or electron microscopy is challenging. We present a new approach that combines the point accumulation in nanoscale topography (PAINT) super-resolution method with a newly synthesized Nile Red probe (diOHNR) as the fluorescent label. The molecule was modified to undergo a hydrogen bond-assisted interaction with the polyamide phase in the blend due to its two additional hydroxyl groups but preserves the spectral properties of Nile Red. As a result, the localization density of the probe in the PAINT image is 13 times larger at the polyamide phase than at the polyethylene phase, enabling quantitative evaluation of the spatial polyamide/polyethylene distribution down to the nanoscale. The method achieved a spatial resolution of 18.8 nm, and we found that over half of the polyamide particles in a recycled sample were smaller than the optical diffraction limit. Being able to image the blends with nanoscopic resolution can help to optimize the composition and mechanical properties of recycled materials and thus contribute to an increased reuse of plastics.

To monitor adherence to diets and to design and evaluate nutritional interventions, it is essential to obtain objective knowledge about eating behavior. In most research, measures of eating behavior are based on self-reporting, such as 24-h recalls, food records (food diaries) and food frequency questionnaires. Self-reporting is prone to inaccuracies due to inaccurate and subjective recall and other biases. Recording behavior using nonobtrusive technology in daily life would overcome this. Here, we provide an up-to-date systematic overview encompassing all (close-to) publicly or commercially available technologies to automatically record eating behavior in real-life settings. A total of 1328 studies were screened and, after applying defined inclusion and exclusion criteria, 122 studies were included for in-depth evaluation. Technologies in these studies were categorized by what type of eating behavior they measure and which type of sensor technology they use. In general, we found that relatively simple sensors are often used. Depending on the purpose, these are mainly motion sensors, microphones, weight sensors and photo cameras. While several of these technologies are commercially available, there is still a lack of publicly available algorithms that are needed to process and interpret the resulting data. We argue that future work should focus on developing robust algorithms and validating these technologies in real-life settings. Combining technologies (e.g., prompting individuals for self-reports at sensed, opportune moments) is a promising route toward ecologically valid studies of eating behavior.

Introduction: When multiple individuals are presented with narrative movie or audio clips, their electrodermal activity (EDA) and heart rate show significant similarities. Higher levels of such inter-subject physiological synchrony are related with higher levels of attention toward the narrative, as for instance expressed by more correctly answered questions about the narrative. We here investigate whether physiological synchrony in EDA and heart rate during watching of movie clips predicts performance on a subsequent vigilant attention task among participants exposed to a night of total sleep deprivation., Methods: We recorded EDA and heart rate of 54 participants during a night of total sleep deprivation. Every hour from 22:00 to 07:00 participants watched a 10-min movie clip during which we computed inter-subject physiological synchrony. Afterwards, they answered questions about the movie and performed the psychomotor vigilance task (PVT) to capture attentional performance., Results: We replicated findings that inter-subject correlations in EDA and heart rate predicted the number of correct answers on questions about the movie clips. Furthermore, we found that inter-subject correlations in EDA, but not in heart rate, predicted PVT performance. Individuals' mean EDA and heart rate also predicted their PVT performance. For EDA, inter-subject correlations explained more variance of PVT performance than individuals' mean EDA., Discussion: Together, these findings confirm the association between physiological synchrony and attention. Physiological synchrony in EDA does not only capture the attentional processing during the time that it is determined, but also proves valuable for capturing more general changes in the attentional state of monitored individuals., Competing Interests: JE and A-MB declared that they were an editorial board member of Frontiers, at the time of submission. This had no impact on the peer review process and the final decision. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Stuldreher, Maasland, Bottenheft, van Erp and Brouwer.)

Wearable sensors offer new opportunities for the early detection and identification of toxic chemicals in situations where medical evaluation is not immediately possible. We previously found that continuously recorded physiology in guinea pigs can be used for early detection of exposure to an opioid (fentanyl) or a nerve agent (VX), as well as for differentiating between the two. Here, we investigated how exposure to these different chemicals affects the interactions between ECG and respiration parameters as determined by Granger causality (GC). Features reflecting such interactions may provide additional information and improve models differentiating between chemical agents. Traditional respiration and ECG features, as well as GC features, were extracted from data of 120 guinea pigs exposed to VX ( n = 61) or fentanyl ( n = 59). Data were divided in a training set ( n = 99) and a test set ( n = 21). Minimum Redundancy Maximum Relevance (mRMR) and Support Vector Machine (SVM) algorithms were used to, respectively, perform feature selection and train a model to discriminate between the two chemicals. We found that ECG and respiration parameters are Granger-related under healthy conditions, and that exposure to fentanyl and VX affected these relationships in different ways. SVM models discriminated between chemicals with accuracy of 95% or higher on the test set. GC features did not improve the classification compared to traditional features. Respiration features (i.e., peak inspiratory and expiratory flow) were the most important to discriminate between different chemical's exposure. Our results indicate that it may be feasible to discriminate between chemical exposure when using traditional physiological respiration features from wearable sensors. Future research will examine whether GC features can contribute to robust detection and differentiation between chemicals when considering other factors, such as generalizing results across species., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Difrancesco, van Baardewijk, Cornelissen, Varon, Hendriks and Brouwer.)

Individuals that pay attention to narrative stimuli show synchronized heart rate (HR) and electrodermal activity (EDA) responses. The degree to which this physiological synchrony occurs is related to attentional engagement. Factors that can influence attention, such as instructions, salience of the narrative stimulus and characteristics of the individual, affect physiological synchrony. The demonstrability of synchrony depends on the amount of data used in the analysis. We investigated how demonstrability of physiological synchrony varies with varying group size and stimulus duration. Thirty participants watched six 10 min movie clips while their HR and EDA were monitored using wearable sensors (Movisens EdaMove 4 and Wahoo Tickr, respectively). We calculated inter-subject correlations as a measure of synchrony. Group size and stimulus duration were varied by using data from subsets of the participants and movie clips in the analysis. We found that for HR, higher synchrony correlated significantly with the number of answers correct for questions about the movie, confirming that physiological synchrony is associated with attention. For both HR and EDA, with increasing amounts of data used, the percentage of participants with significant synchrony increased. Importantly, we found that it did not matter how the amount of data was increased. Increasing the group size or increasing the stimulus duration led to the same results. Initial comparisons with results from other studies suggest that our results do not only apply to our specific set of stimuli and participants. All in all, the current work can act as a guideline for future research, indicating the amount of data minimally needed for robust analysis of synchrony based on inter-subject correlations.

When two solid objects slide over each other, friction results from the interactions between the asperities of the (invariably rough) surfaces. Lubrication happens when viscous lubricants separate the two surfaces and carry the load such that solid-on-solid contacts are avoided. Yet, even small amounts of low-viscosity lubricants can still significantly lower friction through a process called boundary lubrication. Understanding the origin of the boundary lubricating effect is hampered by challenges in measuring the interfacial properties of lubricants directly between the two surfaces. Here, we use rigidochromic fluorescent probe molecules to measure precisely what happens on a molecular scale during vapor-phase boundary lubrication of a polymer bead-on-glass interface. The probe molecules have a longer fluorescence lifetime in a confined environment, which allows one to measure the area of real contact between rough surfaces and infer the shear stress at the lubricated interfaces. The latter is shown to be proportional to the inverse of the local interfacial free volume determined using the measured fluorescence lifetime. The free volume can then be used in an Eyring-type model as the stress activation volume, allowing to collapse the data of stress as a function of sliding velocity and partial pressure of the vapor phase lubricant. This shows directly that as more boundary lubricant is applied, larger clusters of lubricant molecules become involved in the shear process thereby lowering the friction.

Molecular photoelectrochemical devices are hampered by electron-hole recombination after photoinduced electron transfer, causing losses in power conversion efficiency. Inspired by natural photosynthesis, we demonstrate the use of supramolecular machinery as a strategy to inhibit recombination through an organization of molecular components that enables unbinding of the final electron acceptor upon reduction. We show that preorganization of a macrocyclic electron acceptor to a dye yields a pseudorotaxane that undergoes a fast (completed within ~50 ps) 'ring-launching' event upon electron transfer from the dye to the macrocycle, releasing the anionic macrocycle and thus reducing charge recombination. Implementing this system into p-type dye-sensitized solar cells yielded a 16-fold and 5-fold increase in power conversion efficiency compared to devices based on the two control dyes that are unable to facilitate pseudorotaxane formation. The active repulsion of the anionic macrocycle with concomitant reformation of a neutral pseudorotaxane complex circumvents recombination at both the semiconductor-electrolyte and semiconductor-dye interfaces, enabling a threefold enhancement in hole lifetime., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

In this paper, we present a review of how the various aspects of any study using an eye tracker (such as the instrument, methodology, environment, participant, etc.) affect the quality of the recorded eye-tracking data and the obtained eye-movement and gaze measures. We take this review to represent the empirical foundation for reporting guidelines of any study involving an eye tracker. We compare this empirical foundation to five existing reporting guidelines and to a database of 207 published eye-tracking studies. We find that reporting guidelines vary substantially and do not match with actual reporting practices. We end by deriving a minimal, flexible reporting guideline based on empirical research (Section "An empirically based minimal reporting guideline")., (© 2022. The Author(s).)

When two macroscopic objects touch, the real contact typically consists of multiple surface asperities that are deformed under the pressure that holds the objects together. Application of a shear force makes the objects slide along each other, breaking the initial contacts. To investigate how the microscopic shear force at the asperity level evolves during the transition from static to dynamic friction, we apply a fluorogenic mechanophore to visualize and quantify the local interfacial shear force. When a contact is broken, the shear force is released and the molecules return to their dark state, allowing us to dynamically observe the evolution of the shear force at the sliding contacts. We find that the macroscopic coefficient of friction describes the microscopic friction well, and that slip propagates from the edge toward the center of the macroscopic contact area before sliding occurs. This allows for a local understanding of how surfaces start to slide.

In vivo data are rare but essential for establishing the clinical potential of ruthenium-based photoactivated chemotherapy (PACT) compounds, a new family of phototherapeutic drugs that are activated via ligand photosubstitution. Here a novel trisheteroleptic ruthenium complex [Ru(dpp)(bpy)(mtmp)](PF 6 ) 2 ([2](PF 6 ) 2 , dpp = 4,7-diphenyl-1,10-phenanthroline, bpy = 2,2'-bipyridine, mtmp = 2-methylthiomethylpyridine) was synthesized and its light-activated anticancer properties were validated in cancer cell monolayers, 3D tumor spheroids, and in embryonic zebrafish cancer models. Upon green light irradiation, the non-toxic mtmp ligand is selectively cleaved off, thereby releasing a phototoxic ruthenium-based photoproduct capable notably of binding to nuclear DNA and triggering DNA damage and apoptosis within 24-48 h. In vitro , fifteen minutes of green light irradiation (21 mW cm -2 , 19 J cm -2 , 520 nm) were sufficient to generate high phototherapeutic indexes (PI) for this compound in a range of cancer cell lines including lung (A549), prostate (PC3Pro4), conjunctival melanoma (CRMM1, CRMM2, CM2005.1) and uveal melanoma (OMM1, OMM2.5, Mel270) cancer cell lines. The therapeutic potential of [2](PF 6 ) 2 was further evaluated in zebrafish embryo ectopic (PC3Pro4) or orthotopic (CRMM1, CRMM2) tumour models. The ectopic model consisted of red fluorescent PC3Pro4-mCherry cells injected intravenously (IV) into zebrafish, that formed perivascular metastatic lesions at the posterior ventral end of caudal hematopoietic tissue (CHT). By contrast, in the orthotopic model, CRMM1- and CRMM2-mCherry cells were injected behind the eye where they developed primary lesions. The maximally-tolerated dose (MTD) of [2](PF 6 ) 2 was first determined for three different modes of compound administration: (i) incubating the fish in prodrug-containing water (WA); (ii) injecting the prodrug intravenously (IV) into the fish; or (iii) injecting the prodrug retro-orbitally (RO) into the fish. To test the anticancer efficiency of [2](PF 6 ) 2 , the embryos were treated 24 h after engraftment at the MTD. Optimally, four consecutive PACT treatments were performed on engrafted embryos using 60 min drug-to-light intervals and 90 min green light irradiation (21 mW cm -2 , 114 J cm -2 , 520 nm). Most importantly, this PACT protocol was not toxic to the zebrafish. In the ectopic prostate tumour models, where [2](PF 6 ) 2 showed the highest photoindex in vitro (PI > 31), the PACT treatment did not significantly diminish the growth of primary lesions, while in both conjunctival melanoma orthotopic tumour models, where [2](PF 6 ) 2 showed more modest photoindexes (PI ∼ 9), retro-orbitally administered PACT treatment significantly inhibited growth of the engrafted tumors. Overall, this study represents the first demonstration in zebrafish cancer models of the clinical potential of ruthenium-based PACT, here against conjunctival melanoma., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

Pillar[ n ]arenes are pillar-shaped macrocyclic compounds owing to the methylene bridges linking the para-positions of the units. Owing to their unique pillar-shaped structures, these compounds exhibit various excellent properties compared with other cyclic host molecules, such as versatile functionality using various organic synthesis techniques, substituent-dependent solubility, cavity-size-dependent host-guest properties in organic media, and unit rotation along with planar chiral inversion. These advantages have enabled the high-yield synthesis and rational design of pillar[ n ]arene-based mechanically interlocked molecules (MIMs). In particular, new types of pillar[ n ]arene-based MIMs that can dynamically convert between interlocked and unlocked states through unit rotation have been produced. The highly symmetrical pillar-shaped structures of pillar[ n ]arenes result in simple NMR spectra, which are useful for studying the motion of pillar[ n ]arene wheels in MIMs and creating sophisticated MIMs with higher-order structures. The creation and application of polymeric MIMs based on pillar[ n ]arenes is also discussed.

We investigate the local viscosity of a polymer glass around its glass transition temperature by using environment-sensitive fluorescent molecular rotors embedded in the polymer matrix. The fluorescence of the rotors depends on the local viscosity, and measuring the fluorescence intensity and lifetime of the probe therefore allows us to measure the local free volume in the polymer glass when going through the glass transition. This also allows us to study the local viscosity and free volume when the polymer film is put under an external stress. We find that the film does not flow homogeneously but undergoes shear banding that is visible as a spatially varying free volume and viscosity.

Reflecting the two main prevailing and opposing views on the nature of emotions, emotional responses to food and beverages are typically measured using either (a) a categorical (lexicon-based) approach where users select or rate the terms that best express their food-related feelings or (b) a dimensional approach where they rate perceived food items along the dimensions of valence and arousal. Relating these two approaches is problematic since a response in terms of valence and arousal is not easily expressed in terms of emotions (like happy or disgusted). In this study, we linked the dimensional approach to a categorical approach by establishing mapping between a set of 25 emotion terms (EsSense25) and the valence-arousal space (via the EmojiGrid graphical response tool), using a set of 20 food images. In two 'matching' tasks, the participants first imagined how the food shown in a given image would make them feel and then reported either the emotional terms or the combination of valence and arousal that best described their feelings. In two labeling tasks, the participants first imagined experiencing a given emotion term and then they selected either the foods (images) that appeared capable to elicit that feeling or reported the combination of valence and arousal that best reflected that feeling. By combining (1) the mapping between the emotion terms and the food images with (2) the mapping of the food images to the valence-arousal space, we established (3) an indirect (via the images) mapping of the emotion terms to the valence-arousal space. The results show that the mapping between terms and images was reliable and that the linkages have straightforward and meaningful interpretations. The valence and arousal values that were assigned to the emotion terms through indirect mapping to the valence-arousal space were typically less extreme than those that were assigned through direct mapping.

The absorption of extreme ultraviolet (EUV) radiation by a photoresist strongly depends on its atomic composition. Consequently, elements with a high EUV absorption cross section can assist in meeting the demand for higher photon absorbance by the photoresist to improve the sensitivity and reduce the photon shot noise induced roughness. In this work, we enhanced the EUV absorption of the methacrylic acid ligands of Zn oxoclusters by introducing fluorine atoms. We evaluated the lithography performance of this fluorine-rich material as a negative tone EUV photoresist along with extensive spectroscopic and microscopic studies, providing deep insights into the underlying mechanism. UV-vis spectroscopy studies demonstrate that the presence of fluorine in the oxocluster enhances its stability in the thin films to the ambient atmosphere. However, the EUV photoresist sensitivity ( D 50 ) of the fluorine-rich oxocluster is decreased compared to its previously studied methacrylic acid analogue. Scanning transmission X-ray microscopy and in situ X-ray photoelectron spectroscopy in combination with FTIR and UV-vis spectroscopy were used to gain insights into the chemical changes in the material responsible for the solubility switch. The results support decarboxylation of the ligands and subsequent radical-induced polymerization reactions in the thin film upon EUV irradiation. The rupture of carbon-fluorine bonds via dissociative electron attachment offers a parallel way of generating radicals. The mechanistic insights obtained here will be applicable to other hybrid materials and potentially pave the way for the development of EUV materials with better performance., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Controlling self-assembly of nanocomposites is a fundamental challenge with exciting implications for next-generation advanced functional materials. Precursors for composites can be generated photochemically, but limited insight in the underlying processes has hindered precise hands-on guidance. In this study, light-controlled nucleation and growth is demonstrated for self-assembling composites according to precise user-defined designs. Carbonate is generated photochemically with UV light to steer the precipitation of nanocomposites of barium carbonate nanocrystals and amorphous silica (BaCO 3 /SiO 2 ). Using a custom-built optical setup, the self-assembly process is controlled by optimizing the photogeneration, diffusion, reaction, and precipitation of the carbonate species, using the radius and intensity of the UV-light irradiated area and reaction temperature. Exploiting this control, nucleation is induced and the contours and individual features of the growing composite are sculpted according to micrometer-defined light patterns. Moreover, moving light patterns are exploited to create a constant carbonate concentration at the growth front to draw lines of nanocomposites with constant width over millimeters with micrometer precision. Light-directed generation of local gradients opens previously unimaginable opportunities for guiding self-assembly into functional materials., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Research on brain signals as indicators of a certain attentional state is moving from laboratory environments to everyday settings. Uncovering the attentional focus of individuals in such settings is challenging because there is usually limited information about real-world events, as well as a lack of data from the real-world context at hand that is correctly labeled with respect to individuals' attentional state. In most approaches, such data is needed to train attention monitoring models. We here investigate whether unsupervised clustering can be combined with physiological synchrony in the electroencephalogram (EEG), electrodermal activity (EDA), and heart rate to automatically identify groups of individuals sharing attentional focus without using knowledge of the sensory stimuli or attentional focus of any of the individuals. We used data from an experiment in which 26 participants listened to an audiobook interspersed with emotional sounds and beeps. Thirteen participants were instructed to focus on the narrative of the audiobook and 13 participants were instructed to focus on the interspersed emotional sounds and beeps. We used a broad range of commonly applied dimensionality reduction ordination techniques-further referred to as mappings-in combination with unsupervised clustering algorithms to identify the two groups of individuals sharing attentional focus based on physiological synchrony. Analyses were performed using the three modalities EEG, EDA, and heart rate separately, and using all possible combinations of these modalities. The best unimodal results were obtained when applying clustering algorithms on physiological synchrony data in EEG, yielding a maximum clustering accuracy of 85%. Even though the use of EDA or heart rate by itself did not lead to accuracies significantly higher than chance level, combining EEG with these measures in a multimodal approach generally resulted in higher classification accuracies than when using only EEG. Additionally, classification results of multimodal data were found to be more consistent across algorithms than unimodal data, making algorithm choice less important. Our finding that unsupervised classification into attentional groups is possible is important to support studies on attentional engagement in everyday settings., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Stuldreher, Merasli, Thammasan, van Erp and Brouwer.)

Sexual assaults against women are a leading threat to human rights and public health in the United States. Considering the high rates of sexual revictimization among women and the limited understanding of the mechanisms which fuel this phenomenon, the goal of the present study was to investigate the role of emotion in coping with a hypothetical threat of sexual assault for previously sexually victimized college women. A total of 114 college women with a history of sexual victimization listened to an audio-recording describing a sexual assault scenario and then described how they felt. A qualitative analysis paradigm was used to capture participants' responses in an open-ended, real-time, experiential manner. Data were analyzed using Consensual Qualitative Research-Modified methodology. Four main themes emerged ( Negative Reactions, Indifferent Evaluations, Active Responses , and Cognitive Appraisal of the Situation ), along with various subcategories, demonstrating the variability of women's responses to a sexual assault threat. Many women experienced uncomfortable or distressing emotional reactions to the vignette, primarily through discomfort, but also through anger, anxiety, and being upset. Few women reported experiencing fear, and a small number reported experiencing self-blame. The low endorsement of fear and anger in our high-risk sample indicates emotional dysregulation as a potential mechanism of repeated sexual victimization and a promising target for clinical intervention. Overall, results may inform sexual assault risk reduction efforts and the empowerment of women who have experienced sexual victimization.

Covalent functionalisation with alkyl tails is a common method for supporting molecular catalysts and photosensitisers onto lipid bilayers, but the influence of the alkyl chain length on the photocatalytic performances of the resulting liposomes is not well understood. In this work, we first prepared a series of rhenium-based CO 2 -reduction catalysts [Re(4,4'-(C n H 2n+1 ) 2 -bpy)(CO) 3 Cl] (ReC n ; 4,4'-(C n H 2n+1 ) 2 -bpy=4,4'-dialkyl-2,2'-bipyridine) and ruthenium-based photosensitisers [Ru(bpy) 2 (4,4'-(C n H 2n+1 ) 2 -bpy)](PF 6 ) 2 (RuC n ) with different alkyl chain lengths (n=0, 9, 12, 15, 17, and 19). We then prepared a series of PEGylated DPPC liposomes containing RuC n and ReC n , hereafter noted C n , to perform photocatalytic CO 2 reduction in the presence of sodium ascorbate. The photocatalytic performance of the C n liposomes was found to depend on the alkyl tail length, as the turnover number for CO (TON) was inversely correlated to the alkyl chain length, with a more than fivefold higher CO production (TON=14.5) for the C 9 liposomes, compared to C 19 (TON=2.8). Based on immobilisation efficiency quantification, diffusion kinetics, and time-resolved spectroscopy, we identified the main reason for this trend: two types of membrane-bound RuC n species can be found in the membrane, either deeply buried in the bilayer and diffusing slowly, or less buried with much faster diffusion kinetics. Our data suggest that the higher photocatalytic performance of the C 9 system is due to the higher fraction of the more mobile and less buried molecular species, which leads to enhanced electron transfer kinetics between RuC 9 and ReC 9 ., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Integrating fundamental science in society, with the goal to translate research findings to daily practice, comes with certain challenges. Successfully integrating research projects into society requires (1) good collaboration between scientists and societal stakeholders, (2) collaboration partners with common expectations and goals, and (3) investment in clear communication. Here we describe an integrative research project conducted by a large Dutch consortium that consisted of neuroscientists, psychologists, sociologists, ethicists, teachers, health care professionals and policy makers, focusing on applying cognitive developmental neuroscience for the benefit of youth in education and social safety. We argue that to effectively integrate cognitive developmental neuroscience in society, (1) it is necessary to invest in a well-functioning, diverse and multidisciplinary team involving societal stakeholders and youth themselves from the start of the project. This aids to build a so-called productive interactive network that increases the chances to realize societal impact in the long-term. Additionally, we propose that to integrate knowledge, (2) a different than standard research approach should be taken. When focusing on integration, the ultimate goal of research is not solely to understand the world better, but also to intervene with real-life situations, such as education or (forensic) youth care. To accomplish this goal, we propose an approach in which integration is not only started after the research has been conducted, but taken into account throughout the entire project. This approach helps to create common expectations and goals between different stakeholders. Finally, we argue that (3) dedicating sufficient resources to effective communication, both within the consortium and between scientists and society, greatly benefits the integration of cognitive developmental neuroscience in society., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Vandenbroucke, Crone, Erp, Güroğlu, Hulshoff Pol, de Kogel, Krabbendam, Jansen and Brouwer.)

Extreme ultraviolet (EUV) lithography uses 13.5 nm light to reach the sub-20 nm resolution. However, the process of pattern formation induced by this high-energy light is not well-understood. In this work, we provide an inorganic EUV photoresist with fluorescence properties by introducing a carbazole derivative as a ligand, and we study its effect on the patterning process. Using the fluorescence properties, changes in the emission of the material after EUV exposure could be tracked by means of spectroscopy and microscopy. The resist sensitivity was substantially reduced by the incorporation of the carbazole benzoate ligands, which is attributed to hole trapping and steric hindrance. After EUV irradiation of the resist films, infrared, UV-visible absorption, and fluorescence spectroscopies showed that the carbazole units were still mostly intact, although their fluorescence intensity was lowered. Our work shows that fluorescent labeling can provide relevant mechanistic insights in the patterning process of resists, potentially with a molecular resolution.

We present a table-top extreme ultraviolet (XUV) beamline for measuring time- and frequency-resolved XUV-excited optical luminescence (XEOL) with additional femtosecond-resolution XUV transient absorption spectroscopy functionality. XUV pulses are generated via high-harmonic generation using a near-infrared pulse in a noble gas medium and focused to excite luminescence from a solid sample. The luminescence is collimated and guided into a streak camera where its spectral components are temporally resolved with picosecond temporal resolution. We time-resolve XUV-excited luminescence and compare the results to luminescence decays excited at longer wavelengths for three different materials: (i) sodium salicylate, an often used XUV scintillator; (ii) fluorescent labeling molecule 4-carbazole benzoic (CB) acid; and (iii) a zirconium metal oxo-cluster labeled with CB, which is a photoresist candidate for extreme-ultraviolet lithography. Our results establish time-resolved XEOL as a new technique to measure transient XUV-driven phenomena in solid-state samples and identify decay mechanisms of molecules following XUV and soft-x-ray excitation.

Tetrazines with branched alkoxy substituents are liquids at ambient temperature that despite the high chromophore density retain the bright orange fluorescence that is characteristic of this exceptional fluorophore. Here, we study the photophysical properties of a series of alkoxy-tetrazines in solution and as neat liquids. We also correlate the size of the alkoxy substituents with the viscosity of the liquids. We show using time-resolved spectroscopy that intersystem crossing is an important decay pathway competing with fluorescence, and that its rate is higher for 3,6-dialkoxy derivatives than for 3-chloro-6-alkoxytetrazines, explaining the higher fluorescence quantum yields for the latter. Quantum chemical calculations suggest that the difference in rate is due to the activation energy required to distort the tetrazine core such that the nπ*S1 and the higher-lying ππ*T2 states cross, at which point the spin-orbit coupling exceeding 10 cm-1 allows for efficient intersystem crossing to occur. Femtosecond time-resolved anisotropy studies in solution allow us to measure a positive relationship between the alkoxy chain lengths and their rotational correlation times, and studies in the neat liquids show a fast decay of the anisotropy consistent with fast exciton migration in the neat liquid films.

How we perceive the world is not solely determined by what we sense at a given moment in time, but also by what we processed recently. Here we investigated whether such serial dependencies for emotional stimuli transfer from one modality to another. Participants were presented a random sequence of emotional sounds and images and instructed to rate the valence and arousal of each stimulus (Experiment 1). For both ratings, we conducted an intertrial analysis, based on whether the rating on the previous trial was low or high. We found a positive serial dependence for valence and arousal regardless of the stimulus modality on two consecutive trials. In Experiment 2, we examined whether passively perceiving a stimulus is sufficient to induce a serial dependence. In Experiment 2, participants were instructed to rate the stimuli only on active trials and not on passive trials. The participants were informed that the active and passive trials were presented in alternating order, so that they were able to prepare for the task. We conducted an intertrial analysis on active trials, based on whether the rating on the previous passive trial (determined in Experiment 1) was low or high. For both ratings, we again observed positive serial dependencies regardless of the stimulus modality. We conclude that the emotional experience triggered by one stimulus affects the emotional experience for a subsequent stimulus regardless of their sensory modalities, that this occurs in a bottom-up fashion, and that this can be explained by residual activation in the emotional network in the brain.

Photoresist materials are being optimized for the recently introduced Extreme Ultraviolet (EUV) photolithographic technology. Organometallic compounds are potential candidates for replacing the ubiquitous polymer-based chemically amplified resists. Tin (Sn) has a particularly large absorption cross section for EUV light (13.5 nm, 92 eV), which could lead to a lower required EUV dose for achieving the desired solubility change (improved sensitivity). However, the fundamental interaction between organometallic materials and higher energy photons is poorly understood. In this work, we exposed n -butyltin-oxo cage dications (M 2+ ) in the gas phase to photons in the energy range 4-35 eV to explore their fundamental photoreactivity. Photoproducts were detected using mass spectrometry. Homolytic cleavage of tin-carbon bonds was observed for all photon energies above the onset of electronic absorption at ∼5 eV (∼250 nm), leading to photoproducts which have lost one or more of the attached butyl groups (Bu). Above 12 eV (<103 nm), dissociative photoionization occurred for the dication (M 2+ ), competing with the neutral loss channels. The photoionization threshold is lowered by approximately 2 eV when one counterion (triflate, OTf - or tosylate, OTs - ) is attached to the tin-oxo cage (MOTf + and MOTs + ). This threshold is expected to be even lower if each tin-oxo cage is attached to two counterions, as is the case in a solid film of tin-oxo cages. Addition of counterions also affected the fragmentation pathways; photoexcitation of (MX) + (X = counterion, OTf or OTs) always led to formation of (MX-2Bu) + rather than (MX-Bu) + . MOTs + was much more reactive than MOTf + in terms of reaction products per absorbed photon. A possible explanation for this is proposed, which involves the counterion reacting with the initially formed tin-based radical.

Many drug delivery systems end up in the lysosome because they are built from covalent or kinetically inert supramolecular bonds. To reach other organelles, nanoparticles hence need to either be made from a kinetically labile interaction that allows re-assembly of the nanoparticles inside the cell following endocytic uptake, or, be taken up by a mechanism that short-circuits the classical endocytosis pathway. In this work, the intracellular fate of nanorods that self-assemble via the Pt…Pt interaction of cyclometalated platinum(II) compounds, is studied. These deep-red emissive nanostructures (638 nm excitation, ≈700 nm emission) are stabilized by proteins in cell medium. Once in contact with cancer cells, they cross the cell membrane via dynamin- and clathrin-dependent endocytosis. However, time-dependent confocal colocalization and cellular electron microscopy demonstrate that they directly move to mitochondria without passing by the lysosomes. Altogether, this study suggests that Pt…Pt interaction is strong enough to generate emissive, aggregated nanoparticles inside cells, but labile enough to allow these nanostructures to reach the mitochondria without being trapped in the lysosomes. These findings open new venues to the development of bioimaging nanoplatforms based on the Pt…Pt interaction., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Implicit ('unconscious') approach-avoidance tendencies towards stimuli can be measured using the Approach Avoidance Task (AAT). We recently expanded a toolbox for analyzing the raw data of a novel, mobile version of the AAT (mAAT), that asks participants to move their phone towards their face (pull) or away (push) in response to images presented on the phone. We here tested the mAAT reaction time and the mAAT distance in a study with 71 Dutch participants that were recruited online and performed an experiment without coming to the laboratory. The participants used both the mAAT and (explicit) rating scales to respond to photographic images of food. As hypothesized, the rated wanting, rated valence and mAAT reaction time indicated a preference for palatable over unpalatable food, and for Dutch over Asian food. Additionally, as expected, arousal was rated higher for unpalatable than for palatable food, and higher for Dutch than for Asian food. The mAAT distance indicated that the unpalatable food images were moved across larger distances, regardless of the movement direction (pull or push), compared to the palatable food images; and the Dutch food images were moved across larger distances than the Asian food images. We conclude that the mAAT can be used to implicitly probe approach-avoidance motivation for complex images in the food domain. The new measure of mAAT distance may be used as an implicit measure of arousal. The ratings and the mAAT measures do not reflect the exact same information and may complement each other. Implicit measures, such as mAAT variables, are particularly valuable when response biases that can occur when using explicit ratings are expected.

Early detection of exposure to a toxic chemical, e.g., in a military context, can be life-saving. We propose to use machine learning techniques and multiple continuously measured physiological signals to detect exposure, and to identify the chemical agent. Such detection and identification could be used to alert individuals to take appropriate medical counter measures in time. As a first step, we evaluated whether exposure to an opioid (fentanyl) or a nerve agent (VX) could be detected in freely moving guinea pigs using features from respiration, electrocardiography (ECG) and electroencephalography (EEG), where machine learning models were trained and tested on different sets (across subject classification). Results showed this to be possible with close to perfect accuracy, where respiratory features were most relevant. Exposure detection accuracy rose steeply to over 95% correct during the first five minutes after exposure. Additional models were trained to correctly classify an exposed state as being induced either by fentanyl or VX. This was possible with an accuracy of almost 95%, where EEG features proved to be most relevant. Exposure detection models that were trained on subsets of animals generalized to subsets of animals that were exposed to other dosages of different chemicals. While future work is required to validate the principle in other species and to assess the robustness of the approach under different, realistic circumstances, our results indicate that utilizing different continuously measured physiological signals for early detection and identification of toxic agents is promising.

The macroscopic viscosity of polymer solutions in general differs strongly from the viscosity at the nanometer scale, and the relation between the two can be complicated. To investigate this relation, we use a fluorescent molecular rotor that probes the local viscosity of its molecular environment. For a range of chain lengths and concentrations, the dependence of the fluorescence on the macroscopic viscosity is well described by the classical Förster-Hoffmann (FH) equation, but the value of the FH exponent depends on the polymer chain length. We show that all data can be collapsed onto a master curve by plotting the fluorescence versus polymer concentration, which we explain in terms of the characteristic mesh size of the polymer solution. Using known scaling laws for polymers then allows us to quantitatively explain the relation between the FH exponent and the polymer chain length, allowing us to link the nano- to the macroviscosity.

The present study investigated the potential of implicit physiological measures to provide objective measures of affective food experience in contrast to explicit self-report ratings in a cross-cultural context. Dutch and Thai participants viewed 120 food images portraying universal food image categories (regular and molded food) and cultural food image categories (typically Dutch and Thai food). The universal food images were taken as ground truth high and low valence stimuli, where we assumed no genuine difference in affective experience between nationalities. In contrast, for the cultural food images, we did expect a genuine difference between nationalities. Participants were asked to rate valence, arousal and liking of each food image. In addition, heart rate (HR) and phasic electrodermal activity (EDA) responses to the images were recorded. Typically Asian and Western response biases were found for explicit ratings of regular and molded food with an extreme response style for Dutch, and a middle response style for Thai participants. However, such bias was not observed in HR. For cultural food image categories, HR showed the hypothesized interaction between participant nationality and food image category, reflecting the expected genuine difference between nationalities in affective food experience. Besides presenting participants with images, we also asked participants to taste typically Thai and Dutch drinks. Similar to images, a significant interaction between participant nationality and cultural food category was found for HR. An interaction was also found for sip size, while this was not seen in explicit measures. We attribute this to differences in the moment that these measures were taken. In this study, phasic EDA did not appear to be a sensitive measure of affective food experience, possibly since stimuli mostly differed in valence rather than arousal. To conclude, our study constitutes an example where cultural bias negatively affected the accuracy of self-reports, and only the implicit physiological measures followed the prior expectations of genuine food experience, indicating the potential of these measures to study cross-cultural food experience., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Kaneko, Stuldreher, Reuten, Toet, van Erp and Brouwer.)

Fluorescent molecular rotors have been used for measurements of local mobility on molecular length scales, for example to determine viscosity, and for the visualization of contact between two surfaces. In the present work, we deepen our insight into the excited-state deactivation kinetics and mechanics of dicyanodihydrofuran-based molecular rotors. We extend the scope of the use of this class of rotors for contact sensing with a red-shifted member of the family. This allows for contact detection with a range of excitation wavelengths up to ∼600 nm. Steady-state fluorescence shows that the fluorescence quantum yield of these rotors depends not only on the rigidity of their environment, but - under certain conditions - also on its polarity. While excited state decay via rotation about the exocyclic double bond is rapid in nonpolar solvents and twisting of a single bond allows for fast decay in polar solvents, the barriers for both processes are significant in solvents of intermediate polarity. This effect may also occur in other molecular rotors, and it should be considered when applying such molecules as local mobility probes., (© 2020 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)

Interpersonal physiological synchrony (PS), or the similarity of physiological signals between individuals over time, may be used to detect attentionally engaging moments in time. We here investigated whether PS in the electroencephalogram (EEG), electrodermal activity (EDA), heart rate and a multimodal metric signals the occurrence of attentionally relevant events in time in two groups of participants. Both groups were presented with the same auditory stimulus, but were instructed to attend either to the narrative of an audiobook (audiobook-attending: AA group) or to interspersed emotional sounds and beeps (stimulus-attending: SA group). We hypothesized that emotional sounds could be detected in both groups as they are expected to draw attention involuntarily, in a bottom-up fashion. Indeed, we found this to be the case for PS in EDA or the multimodal metric. Beeps, that are expected to be only relevant due to specific "top-down" attentional instructions, could indeed only be detected using PS among SA participants, for EDA, EEG and the multimodal metric. We further hypothesized that moments in the audiobook accompanied by high PS in either EEG, EDA, heart rate or the multimodal metric for AA participants would be rated as more engaging by an independent group of participants compared to moments corresponding to low PS. This hypothesis was not supported. Our results show that PS can support the detection of attentionally engaging events over time. Currently, the relation between PS and engagement is only established for well-defined, interspersed stimuli, whereas the relation between PS and a more abstract self-reported metric of engagement over time has not been established. As the relation between PS and engagement is dependent on event type and physiological measure, we suggest to choose a measure matching with the stimulus of interest. When the stimulus type is unknown, a multimodal metric is most robust., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2020 Stuldreher, Thammasan, van Erp and Brouwer.)

Emotional state during food consumption is expected to affect food pleasantness. We hypothesize that a negative emotional state reduces food pleasantness and more so for novel foods than for familiar foods because novel foods have not yet been associated with previous emotions. Furthermore, we expect this effect to be stronger when judging the food again from memory without tasting. We induced a positive emotional state in 34 participants by telling them that they earned a monetary bonus and induced a negative emotional state in 35 other participants by subjecting them to a social stress test. After this emotion induction, both groups tasted and rated a (for them) novel soup (sumashi soup) and a familiar soup (vegetable soup). Several explicit and implicit measures of food pleasantness (rated valence, EsSense25, willingness-to-take-home and sip size) indicated that while the negative emotion group did not experience the soups as less pleasant than the positive emotion group, there was an interaction between food familiarity and emotional group. The positive emotion group experienced novel and familiar soups as equally pleasant, whereas the negative emotion group experienced the novel soup as relatively unpleasant and the familiar soup as pleasant. The latter result is consistent with a comforting effect of a familiar taste in a stressful situation. This effect remained in the ratings given 1 week later based on memory and even after retasting. Our results show that emotional state affects food pleasantness differently for novel and familiar foods and that such an effect can be robust., (Copyright © 2020 Kaneko, Brouwer, Hogervorst, Toet, Kallen and van Erp.)

Measuring psychophysiological signals of adolescents using unobtrusive wearable sensors may contribute to understanding the development of emotional disorders. This study investigated the feasibility of measuring high quality physiological data and examined the validity of signal processing in a school setting. Among 86 adolescents, a total of more than 410 h of electrodermal activity (EDA) data were recorded using a wrist-worn sensor with gelled electrodes and over 370 h of heart rate data were recorded using a chest-strap sensor. The results support the feasibility of monitoring physiological signals at school. We describe specific challenges and provide recommendations for signal analysis, including dealing with invalid signals due to loose sensors, and quantization noise that can be caused by limitations in analog-to-digital conversion in wearable devices and be mistaken as physiological responses. Importantly, our results show that using toolboxes for automatic signal preprocessing, decomposition, and artifact detection with default parameters while neglecting differences between devices and measurement contexts yield misleading results. Time courses of students' physiological signals throughout the course of a class were found to be clearer after applying our proposed preprocessing steps.