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Background: Concussions damage neurologic tissue, increasing release of intercellular proteins including phosphorylated Tau (pTau) and neurofilament light (NfL). Disrupted sleep from a concussion negatively impacts the ability of the glymphatic system to remove cellular waste from the brain., Objective: The purpose of this study was to determine if enhancing sleep using Cognitive Behavioral Therapy for Insomnia (CBT-I) impacts pTau and NFL levels following a concussion., Methods: This is pre/post intervention analysis of a larger wait-list control study. Participants had their blood sampled pre/post the CBT-I intervention which was analyzed using SIMOA analytics. Paired sampling statistics and linear regression models were used to examine how insomnia severity impacts pTau181 and NfL., Results: Twenty-eight participants were enrolled in this study. Age and baseline protein level were significantly associated with post-intervention protein levels, but post-intervention insomnia severity was not associated with post-intervention protein levels. About 50% of participants that had clinically meaningful change in insomnia and had a reduction in their NfL and pTau181 values., Conclusions: Post-intervention insomnia was not associated with post-intervention NfL or pTau. Yet, on an individual level, ~50% of participants had a clinically meaningful change in insomnia and reduced level of NfL and pTau 18.1., Clinical Trial Registration: NCT04885205 https://clinicaltrials.gov., (© The Author(s) 2024. Published by Oxford University Press.)

All humans have the occupational right to sleep; therefore, occupational therapy practitioners must prioritize sleep with their clients. In this column, we identify ways to incorporate sleep health into the education and training of occupational therapy practitioners. This starts with identifying entry-level and continuing education opportunities to proclaim sleep as an occupation and a basic biological need. Current practitioners must recognize that sleep health is multidisciplinary, and existing interventions can help clients achieve good sleep health throughout their lifespan. Given the paucity of sleep research in occupational therapy, the potential exists to investigate new, occupation-based assessments and interventions. We provide specific approaches to expand sleep and sleep health knowledge in occupational therapy education, practice, and research., (Copyright © 2024 by the American Occupational Therapy Association, Inc.)

Aim: Whereas the prevalence of lymph node level (LNL) involvement in oral cavity squamous cell carcinomas (OCSCC) has been reported, the details of lymphatic progression patterns are insufficiently quantified. We investigate how the risk of metastases in each LNL depends on the involvement of adjacent LNLs, T-category, subsite, primary tumor lateralization, and other risk factors., Methods: We retrospectively analyzed patients with newly diagnosed OCSCC from two institutions, totaling 348 patients. Involvement of LNLs I-V was recorded individually based on pathology after neck dissection with clinicopathological factors. The dataset is publicly available in a previously developed web-app, which allows querying patients with specific combinations of co-involved LNLs and tumor characteristics., Results: Ipsilateral involvement prevalence of levels I-III was higher for advanced T-category (T3/T4) patients (32 %, 38 %, 14 %) compared to early (T1/T2) patients (14 %, 23 %, 11 %). Involvement of level I increased the involvement probability in levels II and III. Similarly, involvement of level II increased the involvement probability in levels I and III. However, there was significant isolated involvement of level I or II. Advanced nodal involvement (>1 LNL involved) was more frequent for patients with extracapsular extension. Overall contralateral involvement in levels I-III was 7 %, 4 %, 3 % and more frequent for more advanced ipsilateral involvement and for midline-crossing tumors. Involvement of levels IV and V was rare: 3 % ipsilateral and 1 % contralateral in both levels., Conclusions: Detailed quantification of LNL involvement in OCSCC depending on involvement of adjacent LNLs and clinicopathological factors may allow further personalizing guidelines on elective nodal treatment., Competing Interests: Declaration of competing interest 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., (Copyright © 2024 The Author(s). Published by Elsevier B.V. All rights reserved.)

NMR field cycling relaxometry is a powerful method for determining the rotational and translational dynamics of ions, molecules, and dissolved particles. This is in particular true for ionic liquids (ILs) in which both ions carry NMR sensitive nuclei. In the IL triethylammonium bis(trifluoromethanesulfonyl)imide ([TEA][NTf 2 ]), there are 1 H nuclei at the [TEA] + cations and 19 F nuclei at the [NTf 2 ] - anions. Moreover, the high viscosity of this IL leads to frequency-dependent relaxation rates, leaving the so-called extreme narrowing regime. Both the rotational and the translational dynamics of the constituents of ILs can be obtained by separating the contributions of intra- and intermolecular relaxation rates. In particular, the translational dynamics can be obtained separately by applying the so-called "low-frequency approach" (LFA), utilizing the fact that the change in the total relaxation rates at low frequencies results solely from translational motions. However, for systems containing multiple NMR active nuclei, heteronuclear interactions can also affect their relaxation rates. For [TEA][NTf 2 ], the intermolecular relaxation rate is either the sum of 1 H- 1 H cation-cation and 1 H- 19 F cation-anion interactions or the sum of 19 F- 19 F anion-anion and 19 F- 1 H anion-cation interactions. Due to the lack of available experimental information, the 1 H- 19 F heteronuclear intermolecular contribution has often been neglected in the past, assuming it to be negligible. Employing a suitable set of ILs and by making use of isotopic H/D substitution, we show that the 1 H- 19 F heteronuclear intermolecular contribution in fact cannot be neglected and that the LFA cannot be applied to the total 1 H and total 19 F relaxation rates.

A promising CO2 sorbent based on the [Emim][Gly]/silica gel composite has been studied. Absorption experiments have shown that the optimum loading of [Emim][Gly] ionic liquid in silica gel is 40 wt%. The 2-step process CO2 binding mechanism in [Emim][Gly] has been proposed based on the results of absorption experiments, 2H NMR spectroscopy and ab-initio calculations. The impact of CO2 on the microscopic viscosity and the dynamical melting of ionic liquid has been thoroughly investigated. 2H NMR spectroscopy has revealed that CO2 strongly binds cation and anion in [Emim][Gly], forcing them to move in a correlated fashion., (© 2024 Wiley‐VCH GmbH.)

Objective: To analyze the correlation between arm muscle area and handgrip strength among postmenopausal community dwelling low-income women in order to provide an easy anthropometric indicator to assess muscle mass quantity and quality., Methods: This was a cross-sectional study involving postmenopausal women ( n  = 171) from three urban-marginal communities of Guayaquil, Ecuador. Corrected arm muscle area was calculated using the Frisancho formula. Dynapenia was defined as HGS < 16 kg. Spearman's correlation coefficient was calculated at a 5% significance level to test the correlation between corrected arm muscle area and handgrip strength., Results: Median (interquartile range: IQR) age of the sample was 72.0 years (17.0). The median of corrected arm muscle area was 34.8 cm 2 (20.7). The overall prevalence of dynapenia was 57.9% ( n  = 99). There was a significant decreasing trend with age regarding all anthropometric characteristics and handgrip strength, as well as a higher prevalence of dynapenia with age. For the whole sample, a statistically significant positive correlation was found between corrected arm muscle area and handgrip strength [ r  = 0.267; p  < .001]., There was a significant yet weak positive correlation between corrected arm muscle area and handgrip strength in this postmenopausal sample. There is a need for additional research in this regard.

In this work the green synthesis of gold nanoparticles (Au-NPs) using the oxidoreductive enzymes Myriococcum thermophilum cellobiose dehydrogenase (Mt CDH), Glomerella cingulata glucose dehydrogenase (Gc GDH), and Aspergillus niger glucose oxidase (An GOX)) as bioreductants was investigated. The influence of reaction conditions on the synthesis of Au-NPs was examined and optimised. The reaction kinetics and the influence of Au ions on the reaction rate were determined. Based on the kinetic study, the mechanism of Au-NP synthesis was proposed. The Au-NPs were characterized by UV-Vis spectroscopy and transmission electron microscopy (TEM). The surface plasmon resonance (SPR) absorption peaks of the Au-NPs synthesised with Mt CDH and Gc GDH were observed at 535 nm, indicating an average size of around 50 nm. According to the image analysis performed on a TEM micrograph, the Au-NPs synthesized with Gc GDH have a spherical shape with an average size of 2.83 and 6.63 nm after 24 and 48 h of the reaction, respectively. KEY POINTS: • The Au NPs were synthesised by the action of enzymes CDH and GDH. • The synthesis of Au-NPs by CDH is related to the oxidation of cellobiose. • The synthesis of Au-NPs by GDH was not driven by the reaction kinetic., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The elective clinical target volume (CTV-N) in oropharyngeal squamous cell carcinoma (OPSCC) is currently based mostly on the prevalence of lymph node metastases in different lymph node levels (LNLs) for a given primary tumor location. We present a probabilistic model for ipsilateral lymphatic spread that can quantify the microscopic nodal involvement risk based on an individual patient's T-category and clinical involvement of LNLs at diagnosis. We extend a previously published hidden Markov model (HMM), which models the LNLs (I, II, III, IV, V, and VII) as hidden binary random variables (RVs). Each represents a patient's true state of lymphatic involvement. Clinical involvement at diagnosis represents the observed binary RVs linked to the true state via sensitivity and specificity. The primary tumor and the hidden RVs are connected in a graph. Each edge represents the conditional probability of metastatic spread per abstract time-step, given disease at the edge's starting node. To learn these probabilities, we draw Markov chain Monte Carlo samples from the likelihood of a dataset (686 OPSCC patients) from three institutions. We compute the model evidence using thermodynamic integration for different graphs to determine which describes the data best.The graph maximizing the model evidence connects the tumor to each LNL and the LNLs I through V in order. It predicts the risk of occult disease in level IV is below 5% if level III is clinically negative, and that the risk of occult disease in level V is below 5% except for advanced T-category (T3 and T4) patients with clinical involvement of levels II, III, and IV. The provided statistical model of nodal involvement in OPSCC patients trained on multi-institutional data may guide the design of clinical trials on volume-deescalated treatment of OPSCC and contribute to more personal guidelines on elective nodal treatment., (© 2024. The Author(s).)

Objective: Cognitive behavioral therapy for insomnia (CBT-I) is the gold standard treatment for insomnia, but there is limited evidence on the treatment effect of CBT-I in individuals after a concussion. Therefore, the main purpose of this study was to evaluate the treatment effect of CBT-I on sleep outcomes and postconcussion symptoms., Setting: This study was conducted at an academic institution. The CBT-I sessions were conducted using a teleconferencing system (Zoom)., Participants: Participants were eligible to participate if they were at least 4 weeks post- concussion, aged 18 to 64 years, and scored 10 or more on the Insomnia Severity Index. A total of 40 people were enrolled; 32 participants were included in analyses., Design: This was a randomized controlled wait-list study. Participants were randomized into starting the CBT-I intervention immediately after the baseline assessment or into the wait-list group for 6 weeks before starting CBT-I. Assessments were performed at baseline, 6, 12, and 18 weeks., Main Measures: The primary outcome was the Insomnia Severity Index. Secondary measures included the Pittsburg Sleep Quality Index, Post-Concussion Symptom Scale, and Beck Depression and Anxiety Inventories. Statistical analyses included a repeated-measures analysis of variance, t tests, and mixed linear regression modeling., Results: There was a group-by-time interaction for the sleep outcomes but not for the concussion or mood outcomes. Differences were seen between groups on sleep outcomes, symptom severity, and depression. The treatment effect was maintained following CBT-I for all outcomes. Improvement in sleep outcomes was predictive of improvement in postconcussion symptom severity and number of symptoms., Conclusions: CBT-I reduces insomnia in individuals with concussions, and improved sleep was associated with lower postconcussion and mood symptoms. These effects were maintained 6 to 12 weeks following the intervention., Competing Interests: The authors declare no conflicts of interests., (Copyright © 2024 Wolters Kluwer Health, Inc. All rights reserved.)

Intermolecular interactions determine whether matter sticks together, gases condense into liquids, or liquids freeze into solids. The most prominent example is hydrogen bonding in water, responsible for the anomalous properties in the liquid phase and polymorphism in ice. The physical properties are also exceptional for ionic liquids (ILs), wherein a delicate balance of Coulomb interactions, hydrogen bonds, and dispersion interactions results in a broad liquid range and the vaporization of ILs as ion pairs. In this study, we show that strong, local, and directional hydrogen bonds govern the structures and arrangements in the solid, liquid, and gaseous phases of carboxyl-functionalized ILs. For that purpose, we explored the H-bonded motifs by X-ray diffraction and attenuated total reflection (ATR) infrared (IR) spectroscopy in the solid state, by ATR and transmission IR spectroscopy in the liquid phase, and by cryogenic ion vibrational predissociation spectroscopy (CIVPS) in the gaseous phase at low temperature. The analysis of the CO stretching bands reveals doubly hydrogen-bonded cationic dimers (c═c), resembling the archetype H-bond motif known for carboxylic acids. The like-charge doubly hydrogen-bonded ion pairs are present in the crystal structure of the IL, survive phase transition into the liquid state, and are still present in the gaseous phase even in (2,1) complexes wherein one counterion is removed and repulsive Coulomb interaction increased. The interpretation of the vibrational spectra is supported by quantum chemical methods. These observations have implications for the fundamental nature of the hydrogen bond between ions of like charge.

Background: Cellobiose dehydrogenase (CDH) is an extracellular fungal oxidoreductase with multiple functions in plant biomass degradation. Its primary function as an auxiliary enzyme of lytic polysaccharide monooxygenase (LPMO) facilitates the efficient depolymerization of cellulose, hemicelluloses and other carbohydrate-based polymers. The synergistic action of CDH and LPMO that supports biomass-degrading hydrolases holds significant promise to harness renewable resources for the production of biofuels, chemicals, and modified materials in an environmentally sustainable manner. While previous phylogenetic analyses have identified four distinct classes of CDHs, only class I and II have been biochemically characterized so far., Results: Following a comprehensive database search aimed at identifying CDH sequences belonging to the so far uncharacterized class III for subsequent expression and biochemical characterization, we have curated an extensive compilation of putative CDH amino acid sequences. A sequence similarity network analysis was used to cluster them into the four distinct CDH classes. A total of 1237 sequences encoding putative class III CDHs were extracted from the network and used for phylogenetic analyses. The obtained phylogenetic tree was used to guide the selection of 11 cdhIII genes for recombinant expression in Komagataella phaffii. A small-scale expression screening procedure identified a promising cdhIII gene originating from the plant pathogen Fusarium solani (FsCDH), which was selected for expression optimization by signal peptide shuffling and subsequent production in a 5-L bioreactor. The purified FsCDH exhibits a UV-Vis spectrum and enzymatic activity similar to other characterized CDH classes., Conclusion: The successful production and functional characterization of FsCDH proved that class III CDHs are catalytical active enzymes resembling the key properties of class I and class II CDHs. A detailed biochemical characterization based on the established expression and purification strategy can provide new insights into the evolutionary process shaping CDHs and leading to their differentiation into the four distinct classes. The findings have the potential to broaden our understanding of the biocatalytic application of CDH and LPMO for the oxidative depolymerization of polysaccharides., (© 2024. The Author(s).)

Hydroxy functionalization of cations in ionic liquids (ILs) can lead to formation of hydrogen bonds between their OH groups, resulting in so-called (c-c) H-bonds. Thereby, the (c-c) H-bonds compete with regular H-bonds (c-a) between the OH groups and the anions. Polarizable cations, weakly interacting anions, and long alkyl chains at the cation support the propensity for the formation of (c-c) H-bonds. At low temperatures, the equilibrium between (c-c) and (c-a) H-bonds is strongly shifted in favor of the cation-cation interaction. Herein, we clarify the pressure dependence on (c-c) and (c-a) H-bond distributions in the IL 1-(2-hydroxyethyl)-3-methylimidazolium hexafluorophosphate [HOC 2 C 1 Im][PF 6 ], in mixtures of [HOC 2 C 1 Im][PF 6 ] with the nonhydroxy-functionalized IL 1-propyl-3-methylimidazolium hexafluorophosphate [C 3 C 1 Im][PF 6 ] and in [HOC 2 C 1 Im][PF 6 ] including trace amounts of water. The infrared (IR) spectra provide clear evidence that the (c-c) H-bonds diminish with increasing pressure in favor of the (c-a) H-bonds. Adding trace amounts of water results in enhanced (c-c) clustering due to cooperative effects. At ambient pressure, the water molecules are involved in the (c-c) H-bond motifs. Increasing pressure leads to squeezing them out of H-bond clusters, finally resulting in demixing of water and the IL at the microscopic level.

Lytic polysaccharide monooxygenases (LPMOs) catalyze the oxidative cleavage of glycosidic bonds in recalcitrant polysaccharides, such as cellulose and chitin, using a single copper cofactor bound in a conserved histidine brace with a more variable second coordination sphere. Cellulose-active LPMOs in the fungal AA9 family and in a subset of bacterial AA10 enzymes contain a His-Gln-Tyr second sphere motif, whereas other cellulose-active AA10s have an Arg-Glu-Phe motif. To shine a light on the impact of this variation, we generated single, double, and triple mutations changing the His 216 -Gln 219 -Tyr 221 motif in cellulose- and chitin-oxidizing Ma AA10B toward Arg-Glu-Phe. These mutations generally reduced enzyme performance due to rapid inactivation under turnover conditions, showing that catalytic fine-tuning of the histidine brace is complex and that the roles of these second sphere residues are strongly interconnected. Studies of copper reactivity showed remarkable effects, such as an increase in oxidase activity following the Q219E mutation and a strong dependence of this effect on the presence of Tyr at position 221. In reductant-driven reactions, differences in oxidase activity, which lead to different levels of in situ generated H 2 O 2 , correlated with differences in polysaccharide-degrading ability. The single Q219E mutant displayed a marked increase in activity on chitin in both reductant-driven reactions and reactions fueled by exogenously added H 2 O 2 . Thus, it seems that the evolution of substrate specificity in LPMOs involves both the extended substrate-binding surface and the second coordination sphere., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Oxidoreductases have evolved tyrosine/tryptophan pathways that channel highly oxidizing holes away from the active site to avoid damage. Here we dissect such a pathway in a bacterial LPMO, member of a widespread family of C-H bond activating enzymes with outstanding industrial potential. We show that a strictly conserved tryptophan is critical for radical formation and hole transference and that holes traverse the protein to reach a tyrosine-histidine pair in the protein's surface. Real-time monitoring of radical formation reveals a clear correlation between the efficiency of hole transference and enzyme performance under oxidative stress. Residues involved in this pathway vary considerably between natural LPMOs, which could reflect adaptation to different ecological niches. Importantly, we show that enzyme activity is increased in a variant with slower radical transference, providing experimental evidence for a previously postulated trade-off between activity and redox robustness., (© 2024. The Author(s).)

Main Conclusion: Upon systemic S. indica colonization in split-root system cyst and root-knot nematodes benefit from endophyte-triggered carbon allocation and altered defense responses what significantly facilitates their development in A. thaliana. Serendipita indica is an endophytic fungus that establishes mutualistic relationships with different plants including Arabidopsis thaliana. It enhances host's growth and resistance to different abiotic and biotic stresses such as infestation by the cyst nematode Heterodera schachtii (CN). In this work, we show that S. indica also triggers similar direct reduction in development of the root-knot nematode Meloidogyne javanica (RKN) in A. thaliana. Further, to mimick the natural situation occurring frequently in soil where roots are unequally colonized by endophytes we used an in vitro split-root system with one half of A. thaliana root inoculated with S. indica and the other half infected with CN or RKN, respectively. Interestingly, in contrast to direct effects, systemic effects led to an increase in number of both nematodes. To elucidate this phenomenon, we focused on sugar metabolism and defense responses in systemic non-colonized roots of plants colonized by S. indica. We analyzed the expression of several SUSs and INVs as well as defense-related genes and measured sugar pools. The results show a significant downregulation of PDF1.2 as well as slightly increased sucrose levels in the non-colonized half of the root in three-chamber dish. Thus, we speculate that, in contrast to direct effects, both nematode species benefit from endophyte-triggered carbon allocation and altered defense responses in the systemic part of the root, which promotes their development. With this work, we highlight the complexity of this multilayered tripartite relationship and deliver new insights into sugar metabolism and plant defense responses during S. indica-nematode-plant interaction., (© 2024. The Author(s).)

The spatial and temporal distributions of proteins are critical to protein function, but cannot be directly assessed by measuring protein bundance. Here we describe a mass spectrometry-based proteomics strategy, Simultaneous Proteome Localization and Turnover (SPLAT), to measure concurrently protein turnover rates and subcellular localization in the same experiment. Applying the method, we find that unfolded protein response (UPR) has different effects on protein turnover dependent on their subcellular location in human AC16 cells, with proteome-wide slowdown but acceleration among stress response proteins in the ER and Golgi. In parallel, UPR triggers broad differential localization of proteins including RNA-binding proteins and amino acid transporters. Moreover, we observe newly synthesized proteins including EGFR that show a differential localization under stress than the existing protein pools, reminiscent of protein trafficking disruptions. We next applied SPLAT to an induced pluripotent stem cell derived cardiomyocyte (iPSC-CM) model of cancer drug cardiotoxicity upon treatment with the proteasome inhibitor carfilzomib. Paradoxically, carfilzomib has little effect on global average protein half-life, but may instead selectively disrupt sarcomere protein homeostasis. This study provides a view into the interactions of protein spatial and temporal dynamics and demonstrates a method to examine protein homeostasis regulations in stress and drug response., (© 2024. The Author(s).)

Protein glycosylation, a complex and heterogeneous post-translational modification that is frequently dysregulated in disease, has been difficult to analyse at scale. Here we report a data-independent acquisition technique for the large-scale mass-spectrometric quantification of glycopeptides in plasma samples. The technique, which we named 'OxoScan-MS', identifies oxonium ions as glycopeptide fragments and exploits a sliding-quadrupole dimension to generate comprehensive and untargeted oxonium ion maps of precursor masses assigned to fragment ions from non-enriched plasma samples. By applying OxoScan-MS to quantify 1,002 glycopeptide features in the plasma glycoproteomes from patients with COVID-19 and healthy controls, we found that severe COVID-19 induces differential glycosylation in IgA, haptoglobin, transferrin and other disease-relevant plasma glycoproteins. OxoScan-MS may allow for the quantitative mapping of glycoproteomes at the scale of hundreds to thousands of samples., (© 2023. The Author(s).)

Calixarenes, as novel organic materials, can play a pivotal role in the development of high-performance nonlinear optical materials due to the ease of design and fabrication. In this study, DFT simulations were employed to investigate the geometric, electronic, and NLO responses of calix[4]arene doped with Li 3 O, Na 3 O, and K 3 O superalkalis. The computed values of the vertical ionization energies and interaction energies indicate the chemical and thermodynamic stabilities of the targeted M 3 O@calix[4]arene complexes. The corresponding energy gaps (2.01 to 3.49 eV) are notably reduced, indicating the semiconductor nature of the materials. Surprisingly, the M 3 O@calix[4]arene complexes exhibit transparency in the UV/visible range as the absorption peaks are shifted in the near infrared (NIR) region. The highest values of 5.9 × 10 5 a.u. and 2.3 × 10 8 a.u. for the respective first and second hyperpolarizabilities are observed for Na 3 O@calix[4]arene. Furthermore, the Na 3 O@calix[4]arene complex exhibits maximum values of 2.3 × 10 5 a.u. for second harmonic generation (SHG) and (K 3 O@calix[4]arene) 2.3 × 10 6 a.u. for the electro-optical Pockels effect (EOPE) at 1064 nm. Similarly, approximations are made for the dynamic second hyperpolarizability coefficients (EOKE and EFISHG) at different wavelengths. Notably, the Na 3 O@calix[4]arene complex demonstrates the highest quadratic nonlinear refractive index ( n 2 ) of 9.5 × 10 -15 cm 2 W -1 at 1064 nm. This research paves the way for the development of stable calix[4]arenes doped with superalkalis, leading to an improved nonlinear optical (NLO) response.

We present a computational framework for reliably determining the frequency-dependent intermolecular and intramolecular nuclear magnetic resonance (NMR) dipole-dipole relaxation rates of spin 1/2 nuclei from Molecular Dynamics (MD) simulations. This approach avoids the alterations caused by the well-known finite-size effects of translational diffusion. Moreover, a procedure is derived to control and correct for effects caused by fixed distance-sampling cutoffs and periodic boundary conditions. By construction, this approach is capable of accurately predicting the correct low-frequency scaling behavior of the intermolecular NMR dipole-dipole relaxation rate and thus allows for the reliable calculation of the frequency-dependent relaxation rate over many orders of magnitude. Our approach is based on the utilization of the theory of Hwang and Freed for the intermolecular dipole-dipole correlation function and its corresponding spectral density [L.-P. Hwang and J. H. Freed, J. Chem. Phys. 63, 4017-4025 (1975)] and its combination with data from MD simulations. The deviations from the Hwang and Freed theory caused by periodic boundary conditions and sampling distance cutoffs are quantified by means of random walker Monte Carlo simulations. An expression based on the Hwang and Freed theory is also suggested for correcting those effects. As a proof of principle, our approach is demonstrated by computing the frequency-dependent intermolecular and intramolecular dipolar NMR relaxation rates of 1H nuclei in liquid water at 273 and 298 K based on the simulations of the TIP4P/2005 model. Our calculations are suggesting that the intermolecular contribution to the 1H NMR relaxation rate of the TIP4P/2005 model in the extreme narrowing limit has previously been substantially underestimated., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

Background and Aim: The coronavirus disease 2019 (COVID-19) outbreak deeply affected intensive care units (ICUs). We aimed to explore the main changes in the distribution and characteristics of Swiss ICU patients during the first two COVID-19 waves and to relate these figures with those of the preceding two years., Methods: Using the national ICU registry, we conducted an exploratory study to assess the number of ICU admissions in Switzerland and their changes over time, characteristics of the admissions, the length of stay (LOS) and its trend over time, ICU mortality and changes in therapeutic nursing workload and hospital resources in 2020 and compare them with the average figures in 2018 and 2019., Results: After analysing 242,935 patient records from all 84 certified Swiss ICUs, we found a significant decrease in admissions (-9.6%, corresponding to -8005 patients) in 2020 compared to 2018/2019, with an increase in the proportion of men admitted (61.3% vs 59.6%; p <0.001). This reduction occurred in all Swiss regions except Ticino. Planned admissions decreased from 25,020 to 22,021 in 2020 and mainly affected the neurological/neurosurgical (-14.9%), gastrointestinal (-13.9%) and cardiovascular (-9.3%) pathologies. Unplanned admissions due to respiratory diagnoses increased by 1971 (+25.2%), and those of patients with acute respiratory distress syndrome (ARDS) requiring isolation reached 9973 (+109.9%). The LOS increased by 20.8% from 2.55 ± 4.92 days (median 1.05) in 2018/2019 to 3.08 ± 5.87 days (median 1.11 days; p <0.001), resulting in an additional 19,753 inpatient days. The nine equivalents of nursing manpower use score (NEMS) of the first nursing shift (21.6 ± 9.0 vs 20.8 ± 9.4; p <0.001), the total NEMS per patient (251.0 ± 526.8 vs 198.9 ± 413.8; p <0.01) and mortality (5.7% vs 4.7%; p <0.001) increased in 2020. The number of ICU beds increased from 979 to 1012 (+3.4%), as did the number of beds equipped with mechanical ventilators (from 773 to 821; +6.2%)., Conclusions: Based on a comprehensive national data set, our report describes the profound changes triggered by COVID-19 over one year in Swiss ICUs. We observed an overall decrease in admissions and a shift in admission types, with fewer planned hospitalisations, suggesting the loss of approximately 3000 elective interventions. We found a substantial increase in unplanned admissions due to respiratory diagnoses, a doubling of ARDS cases requiring isolation, an increase in ICU LOS associated with substantial nationwide growth in ICU days, an augmented need for life-sustaining therapies and specific therapeutic resources and worse outcomes.

Biological conversion of plant biomass depends on peroxygenases and peroxidases acting on insoluble polysaccharides and lignin. Among these are cellulose- and hemicellulose-degrading lytic polysaccharide monooxygenases (LPMOs), which have revolutionized our concept of biomass degradation. Major obstacles limiting mechanistic and functional understanding of these unique peroxygenases are their complex and insoluble substrates and the hard-to-measure H 2 O 2 consumption, resulting in the lack of suitable kinetic assays. We report a versatile and robust electrochemical method for real-time monitoring and kinetic characterization of LPMOs and other H 2 O 2 -dependent interfacial enzymes based on a rotating disc electrode for the sensitive and selective quantitation of H 2 O 2 at biologically relevant concentrations. The H 2 O 2 sensor works in suspensions of insoluble substrates as well as in homogeneous solutions. Our characterization of multiple LPMOs provides unprecedented insights into the substrate specificity, kinetics, and stability of these enzymes. High turnover and total turnover numbers demonstrate that LPMOs are fast and durable biocatalysts., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Dataset: We provide a dataset on lymph node metastases in 968 patients with newly diagnosed head and neck squamous cell carcinoma (HNSCC). All patients received neck dissection and we report the number of metastatic versus investigated lymph nodes per lymph node level (LNL) for every individual patient. Additionally, clinicopathological factors including T-category, primary tumor subsite (ICD-O-3 code), age, and sex are reported for all patients. The data is provided as three datasets: Dataset 1 contains 373 HNSCC patients treated at Centre Léon Bérard (CLB), France, with primary tumor location in the oral cavity, oropharynx, hypopharynx, and larynx. Dataset 2 contains 332 HNSCC patients treated at the Inselspital, Bern University Hospital (ISB), Switzerland with primary tumor location in the oral cavity, oropharynx, hypopharynx, and larynx. For these patients, additional information is provided including lateralization of the primary tumor, size and location of the largest metastases, and clinical involvement based on computed tomography (CT), magnetic resonance imaging (MRI), and/or 18FDG-positron emission tomography (PET/CT) imaging. Dataset 3 consists of 263 oropharyngeal SCC patients underlying a previous publication by Bauwens et al. [1], which were treated at CLB. For these patients, additional information including HPV status, lateralization of the primary tumor and clinically diagnosed lymph node involvement is provided., Reuse Potential: The data may be used to quantify the probability of occult lymph node metastases in each LNL, depending on an individual patient's characteristics of the primary tumor and the location of clinically diagnosed lymph node metastases. As such, the data may contribute to further personalize the elective treatment of the neck for HNSCC patients, i.e. definition of the elective clinical target volume (CTV-N) in radiotherapy (RT) and the extent of neck dissection (ND) in surgery. There exists only one similar publicly available dataset that reports clinical involvement per LNL in 287 oropharyngeal SCC patients [2]. The data presented in this article substantially extends the available data, it additionally includes pathologically assessed involvement per LNL, and it provides data for multiple subsites in the head and neck region., (© 2023 The Author(s).)

In multiple sclerosis (MS), mitochondrial alterations appear to contribute to disease progression. The sphingosine-1-phosphate receptor modulator siponimod is approved for treating secondary progressive MS. Its preceding compound fingolimod was shown to prevent oxidative stress-induced alterations in mitochondrial morphology. Here, we assessed the effects of siponimod, compared to fingolimod, on neuronal mitochondria in oxidatively stressed hippocampal slices. We have also advanced the model of chronic organotypic hippocampal slices for live imaging, enabling semi-automated monitoring of mitochondrial alterations. The slices were prepared from B6.Cg-Tg(Thy1-CFP/COX8A)S2Lich/J mice that display fluorescent neuronal mitochondria. They were treated with hydrogen peroxide (oxidative stress paradigm) ± 1 nM siponimod or fingolimod for 24 h. Afterwards, mitochondrial dynamics were investigated. Under oxidative stress, the fraction of motile mitochondria decreased and mitochondria were shorter, smaller, and covered smaller distances. Siponimod partly prevented oxidatively induced alterations in mitochondrial morphology; for fingolimod, a similar trend was observed. Siponimod reduced the decrease in mitochondrial track displacement, while both compounds significantly increased track speed and preserved motility. The novel established imaging and analysis tools are suitable for assessing the dynamics of neuronal mitochondria ex vivo. Using these approaches, we showed that siponimod at 1 nM partially prevented oxidatively induced mitochondrial alterations in chronic brain slices.

ConspectusIonic liquids (ILs) are attracting increasing interest in science and engineering due to their unique properties that can be tailored for specific applications. Clearly, a better understanding of their behavior on the microscopic scale will help to elucidate macroscopic fluid phenomena and thereby promote potential applications. The advantageous properties of these innovative fluids arise from the delicate balance of Coulomb interactions, hydrogen bonding, and dispersion forces. The development of these properties requires a fundamental understanding of the strength, location, and direction of the different types of interactions and their contribution to the overall phase behavior. Contrary to expectations, hydrogen bonding and dispersion interactions have a significant influence on the structure, dynamics, and phase behavior of ILs.The synergy between experimental and theoretical methods has now advanced to a stage where hydrogen bonds and dispersion effects as well as the competition between the two can be studied in detail. In this account, we demonstrate that a suitable combination of spectroscopic, thermodynamic, and theoretical methods enables the detection, dissection, and quantification of noncovalent interactions, even in complex systems such as ionic liquids. This approach encompasses far-infrared vibrational spectroscopy (FIR), various thermodynamic methods for determining enthalpies of vaporization, and quantum chemical techniques that allow us to switch dispersion contributions on or off when calculating the energies and spectroscopic properties of clusters.We briefly discuss these experimental and theoretical methods, before providing various examples illustrating how the mélange of Coulomb interaction, hydrogen bonds, and dispersion forces can be analyzed, and their individual contributions quantified. First, we demonstrated that both hydrogen bonding and dispersion interactions are manifested in the FIR spectra and can be quantified by observed shifts of characteristic spectral signatures. Through the selection of suitable protic ionic liquids (PILs) featuring anions with varying interaction strengths and alkyl chain lengths, we were able to demonstrate that dispersion interactions can compete with hydrogen bonding. The resultant transition enthalpy serves as a measure of the dispersion interaction. Contrary to expectations, PILs possess lower enthalpies of vaporization compared with aprotic ILs (AILs). The reason for this is simple: In protic ILs, ion pairs carry both the hydrogen bond and attractive dispersion between the cation and anion into the gas phase. By utilizing a well-curated set of protic ILs and molecular analogues, we successfully disentangled Coulomb interaction, hydrogen bonding, and dispersion interaction through purely thermodynamic methods.

The main goals and challenges for the life science communities in the Open Science framework are to increase reuse and sustainability of data resources, software tools, and workflows, especially in large-scale data-driven research and computational analyses. Here, we present key findings, procedures, effective measures and recommendations for generating and establishing sustainable life science resources based on the collaborative, cross-disciplinary work done within the EOSC-Life (European Open Science Cloud for Life Sciences) consortium. Bringing together 13 European life science research infrastructures, it has laid the foundation for an open, digital space to support biological and medical research. Using lessons learned from 27 selected projects, we describe the organisational, technical, financial and legal/ethical challenges that represent the main barriers to sustainability in the life sciences. We show how EOSC-Life provides a model for sustainable data management according to FAIR (findability, accessibility, interoperability, and reusability) principles, including solutions for sensitive- and industry-related resources, by means of cross-disciplinary training and best practices sharing. Finally, we illustrate how data harmonisation and collaborative work facilitate interoperability of tools, data, solutions and lead to a better understanding of concepts, semantics and functionalities in the life sciences., (© 2023 The Authors. Published under the terms of the CC BY 4.0 license.)

The price of different truffle types varies according to their culinary value, sometimes by more than a factor of 10. Nonprofessionals can hardly distinguish visually the species within the white or black truffles, making the possibility of food fraud very easy. Therefore, the identification of different truffle species ( Tuber spp.) is an analytical task that could be solved in this study. The polar extract from a total of 80 truffle samples was analyzed by 1 H NMR spectroscopy in combination with chemometric methods covering five commercially relevant species. All classification models were validated applying a repeated nested cross-validation. In direct comparison, the two very similar looking and closely related black representatives Tuber melanosporum and Tuber indicum could be classified 100% correctly. The most expensive truffle Tuber magnatum could be distinguished 100% from the other relevant white truffle Tuber borchii . In addition, signals for a potential Tuber borchii and a potential Tuber melanosporum marker for targeted approaches could be detected, and the corresponding molecules were identified as betaine and ribonate. A model covering all five truffle species Tuber aestivum , Tuber borchii , Tuber indicum , Tuber magnatum , and Tuber melanosporum was able to correctly discriminate between each of the species.

The function of cellobiose dehydrogenase (CDH) in biosensors, biofuel cells, and as a physiological redox partner of lytic polysaccharide monooxygenase (LPMO) is based on its role as an electron donor. Before donating electrons to LPMO or electrodes, an interdomain electron transfer from the catalytic FAD-containing dehydrogenase domain to the electron shuttling cytochrome domain of CDH is required. This study investigates the role of two crucial amino acids located at the dehydrogenase domain on domain interaction and interdomain electron transfer by structure-based engineering. The electron transfer kinetics of wild-type Myriococcum thermophilum CDH and its variants M309A, R698S, and M309A/R698S were analyzed by stopped-flow spectrophotometry and structural effects were studied by small-angle X-ray scattering. The data show that R698 is essential to pull the cytochrome domain close to the dehydrogenase domain and orient the heme propionate group towards the FAD, while M309 is an integral part of the electron transfer pathway - its mutation reducing the interdomain electron transfer 10-fold. Structural models and molecular dynamics simulations pinpoint the action of these two residues on the domain interaction and interdomain electron transfer., (© 2023 The Authors. ChemBioChem published by Wiley-VCH GmbH.)

Observing and quantifying the like-charge attraction in liquids and solutions is still challenging. However, we showed that elusive cation-cation hydrogen bonding may govern the structure and interaction in hydroxyl-functionalized ionic liquids. Therefore, cationic cluster formation depends on the shape, charge distribution, and functionality of the ions. We demonstrated by means of solid-state 2 H NMR spectroscopy that cationic clusters change the structure and dynamics of ionic liquids. With increasing alkyl chain length, we observed two deuteron quadrupole coupling constants for the OD groups, differing by about 30 kHz. The lower value was assigned to the cation-cation interaction, indicating that the average (c-c) hydrogen bonds are stronger than the (c-a) hydrogen bonds between the cation and the anion despite the repulsive and attractive Coulomb interaction in the first and latter cases. Ion mobility could be studied by 2 H NMR spectroscopy, although the deuterons in the hydrogen-bonded clusters underwent fast exchange. Our results also showed that simple relaxation models are not applicable anymore and that anisotropic motion must be considered.

Region-specific meteorological data show that Upper Austria will mainly be affected by increasing temperatures (up to +2.7 °C in 2050) and decreasing precipitation (up to - 27 mm in 2050). Using an interdisciplinary framework, we derive climatic developments and quantify the resulting direct sectoral and macroeconomic impacts for Upper Austria. Based on a set of climate change indicators, sectoral damages are monetized for selected impact chains in forestry, health, agriculture, space heating and cooling, and winter tourism. These damage costs are used as input for ex-ante simulations to quantify the macroeconomic impacts in 2022-2050. The results show an annual decline in gross regional product, accompanied by an annual decline in employment. This study provides a basis for decision making in Upper Austria, as well as in regions with comparable geographical, economic or demographic structures, and highlights the importance of region-specific climate change adaptation strategies., Competing Interests: Declaration of competing interest 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., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

We investigated the bioelectrochemical properties of an FAD-dependent glucose dehydrogenase from Trichoderma virens (TvGDH) and its electrochemical behaviour when immobilized on a graphite electrode. TvGDH was recently shown to have an unusual substrate spectrum and to prefer maltose over glucose as substrate, and hence could be of interest as recognition element in a maltose sensor. In this study, we determined the redox potential of TvGDH, which is -0.268 ± 0.007 V vs. SHE, and advantageously low to be used with many redox mediators or redox polymers. The enzyme was entrapped in, and wired by an osmium redox polymer (poly(1-vinylimidazole-co-allylamine)-{[Os(2,2'-bipyridine) 2 Cl]Cl}) with formal redox potential of +0.275 V vs. Ag|AgCl via poly(ethylene glycol) diglycidyl ether crosslinking onto a graphite electrode. When the TvGDH-based biosensor was tested with maltose it showed a sensitivity of 1.7 μA mM -1 cm -2 , a linear range of 0.5-15 mM, and a detection limit of 0.45 mM. Furthermore, it gave the lowest apparent Michaelis-Menten constant (K M app ) of 19.2 ± 1.5 mM towards maltose when compared to other sugars. The biosensor is also able to detect other saccharides including glucose, maltotriose and galactose, these however also interfere with maltose sensing., Competing Interests: Declaration of Competing Interest 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., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The interdomain electron transfer (IET) between the catalytic flavodehydrogenase domain and the electron-transferring cytochrome domain of cellobiose dehydrogenase (CDH) plays an essential role in biocatalysis, biosensors and biofuel cells, as well as in its natural function as an auxiliary enzyme of lytic polysaccharide monooxygenase. We investigated the mobility of the cytochrome and dehydrogenase domains of CDH, which is hypothesised to limit IET in solution by small angle X-ray scattering (SAXS). CDH from Myriococcum thermophilum (syn. Crassicarpon hotsonii, syn. Thermothelomyces myriococcoides) was probed by SAXS to study the CDH mobility at different pH and in the presence of divalent cations. By comparison of the experimental SAXS data, using pair-distance distribution functions and Kratky plots, we show an increase in CDH mobility at higher pH, indicating alterations of domain mobility. To further visualise CDH movement in solution, we performed SAXS-based multistate modelling. Glycan structures present on CDH partially masked the resulting SAXS shapes, we diminished these effects by deglycosylation and studied the effect of glycoforms by modelling. The modelling shows that with increasing pH, the cytochrome domain adopts a more flexible state with significant separation from the dehydrogenase domain. On the contrary, the presence of calcium ions decreases the mobility of the cytochrome domain. Experimental SAXS data, multistate modelling and previously reported kinetic data show how pH and divalent ions impact the closed state necessary for the IET governed by the movement of the CDH cytochrome domain., (© 2023 The Authors. The FEBS Journal published by John Wiley & Sons Ltd on behalf of Federation of European Biochemical Societies.)

The adsorption method for atmospheric water harvesting (AWH) is considered as a promising heat-driven technology for potable water supply in arid regions. This research is focused on novel composite sorbents based on hygroscopic salts loaded in the pores of MIL-101(Cr) developed for AWH. The composites based on LiCl, LiBr, CaCl 2 , and Ca(NO 3 ) 2 were synthesized and comprehensively studied by SEM, XRD, N 2 adsorption, and thermogravimetric methods. We evidence that the CaCl 2 /MIL-101(Cr) composite demonstrates a high net water uptake of 0.52-0.59 g&#95;(H 2 O)/g&#95;(composite) per cycle under conditions of Saudi Arabia and the Sahara desert as the reference regions with extra-dry climate, which exceeds the appropriate values for other adsorbents. It is shown that water adsorption on the composite cannot be presented as a combination of the adsorption on the components, thus indicating a synergistic effect. A detailed characterization of water coordination, mobility, and hydrogen bonding within the confined CaCl 2 hydrates and salt solution using solid-state 2 H NMR spectroscopy has been performed. It is established that pore confinement promotes a prolonged transition to a dynamically melted state of the hydrated salt and a notable decrease of the melting temperature, which facilitates the molecular transport of water and causes the alteration of sorption properties of CaCl 2 inside MIL-101 pores. Finally, the performance of AWH employing CaCl 2 /MIL-101(Cr) was evaluated in terms of the fractions of water extracted and collected, and the specific energy consumption, demonstrating its high potential for AWH., (© 2023 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Pyruvylation is a biologically versatile but mechanistically unexplored saccharide modification. 4,6-Ketal pyruvylated N-acetylmannosamine within bacterial secondary cell wall polymers serves as a cell wall anchoring epitope for proteins possessing a terminal S-layer homology domain trimer. The pyruvyltransferase CsaB from Paenibacillus alvei served as a model to investigate the structural basis of the pyruvyltransfer reaction by a combination of molecular modelling and site-directed mutagenesis together with an enzyme assay using phosphoenolpyruvate (PEP; donor) and synthetic β-D-ManNAc-(1 → 4)-α-D-GlcNAc-diphosphoryl-11-phenoxyundecyl (acceptor). CsaB protein structure modelling was done using Phyre2 and I-Tasser based on the partial crystal structure of the Schizosaccharomyces pombe pyruvyltransferase Pvg1p and by AlphaFold. The models informed the construction of twelve CsaB mutants targeted at plausible PEP and acceptor binding sites and K M and k cat values were determined to evaluate the mutants, indicating the importance of a loop region for catalysis. R148, H308 and K328 were found to be critical to PEP binding and insight into acceptor binding was obtained from an analysis of Y14 and F16 mutants, confirming the modelled binding sites and interactions predicted using Molecular Operating Environment. These data lay the basis for future mechanistic studies of saccharide pyruvylation as a novel target for interference with bacterial cell wall assembly., (© 2023. Springer Nature Limited.)

Cellobiose dehydrogenase (CDH) is a bioelectrocatalyst that enables direct electron transfer (DET) in biosensors and biofuel cells. The application of this bidomain hemoflavoenzyme for physiological glucose measurements is limited by its acidic pH optimum and slow interdomain electron transfer (IET) at pH 7.5. The reason for this rate-limiting electron transfer step is electrostatic repulsion at the interface between the catalytic dehydrogenase domain and the electron mediating cytochrome domain (CYT). We applied rational interface engineering to accelerate the IET for the pH prevailing in blood or interstitial fluid. Phylogenetic and structural analyses guided the design of 17 variants in which acidic amino acids were mutated at the CYT domain. Five mutations (G71K, D160K, Q174K, D177K, M180K) increased the pH optimum and IET rate. Structure-based analysis of the variants suggested two mechanisms explaining the improvements: electrostatic steering and stabilization of the closed state by hydrogen bonding. Combining the mutations into six combinatorial variants with up to five mutations shifted the pH optimum from 4.5 to 7.0 and increased the IET at pH 7.5 over 12-fold from 0.1 to 1.24 s -1 . While the mutants sustained a high enzymatic activity and even surpassed the IET of the wild-type enzyme, the accumulated positive charges on the CYT domain decreased DET, highlighting the importance of CYT for IET and DET. This study shows that interface engineering is an effective strategy to shift the pH optimum and improve the IET of CDH, but future work needs to maintain the DET of the CYT domain for bioelectronic applications., (© 2023 The Authors. Protein Science published by Wiley Periodicals LLC on behalf of The Protein Society.)

Managing blood glucose can affect important clinical outcomes during the intraoperative phase of surgery. However, currently available instruments for glucose monitoring during surgery are few and not optimized for the specific application. Here we report an attempt to exploit an enzymatic sensor in a vein replica that could continuously monitor glucose level in an authentic human bloodstream. First, detailed investigations of the superficial venous systems of volunteers were carried out using ocular and palpating examinations, as well as advanced ultrasound measurements. Second, a tubular glucose-sensitive biosensor mimicking a venous system was designed and tested. Almost ideal linear dependence of current output on glucose concentration in phosphate buffer saline was obtained in the range 2.2-22.0 mM, whereas the dependence in human plasma was less linear. Finally, the developed biosensor was investigated in whole blood under homeostatic conditions. A specific correlation was found between the current output and glucose concentration at the initial stage of the biodevice operation. However, with time, blood coagulation during measurements negatively affected the performance of the biodevice. When the experimental results were remodeled to predict the response without the influence of blood coagulation, the sensor output closely followed the blood glucose level., Competing Interests: Declaration of Competing Interest 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., (Copyright © 2023 The Author(s). Published by Elsevier B.V. All rights reserved.)

Background: Acute leukemias represent deadly malignancies that require better treatment. As a challenge, treatment is counteracted by a microenvironment protecting dormant leukemia stem cells., Methods: To identify responsible surface proteins, we performed deep proteome profiling on minute numbers of dormant patient-derived xenograft (PDX) leukemia stem cells isolated from mice. Candidates were functionally screened by establishing a comprehensive CRISPR‒Cas9 pipeline in PDX models in vivo., Results: A disintegrin and metalloproteinase domain-containing protein 10 (ADAM10) was identified as an essential vulnerability required for the survival and growth of different types of acute leukemias in vivo, and reconstitution assays in PDX models confirmed the relevance of its sheddase activity. Of translational importance, molecular or pharmacological targeting of ADAM10 reduced PDX leukemia burden, cell homing to the murine bone marrow and stem cell frequency, and increased leukemia response to conventional chemotherapy in vivo., Conclusions: These findings identify ADAM10 as an attractive therapeutic target for the future treatment of acute leukemias., (© 2023. The Author(s).)

Defects fundamentally govern the properties of all real materials. Correlating molecular defects to macroscopic quantities remains a challenge, particularly in the liquid phase. Herein, we report the influence of hydrogen bonds (HB) acting as defects in mixtures of non-hydroxyl-functionalized ionic liquids (ILs) with an increasing concentration of hydroxyl-functionalized ILs. We observed two types of HB defects: The conventional HBs between cation and anion (c-a), and the elusive HBs between cations (c-c) despite the repulsive Coulomb forces. We use neutron diffraction with isotopic substitution in combination with molecular dynamics simulations for measuring the geometry, strength, and distribution of mobile OH defects in the IL mixtures. In principle, this procedure allows relating the number and stability of defects to macroscopic properties such as diffusion, viscosity, and conductivity, which are of utmost importance for the performance of electrolytes in batteries and other electrical devices., (© 2023 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)

Direct bioelectrocatalysis applied in biosensors, biofuel cells, and bioelectrosynthesis is based on an efficient electron transfer between enzymes and electrodes in the absence of redox mediators. Some oxidoreductases are capable of direct electron transfer (DET), while others achieve the enzyme to electrode electron transfer (ET) by employing an electron-transferring domain. Cellobiose dehydrogenase (CDH) is the most-studied multidomain bioelectrocatalyst and features a catalytic flavodehydrogenase domain and a mobile, electron-transferring cytochrome domain connected by a flexible linker. The ET to the physiological redox partner lytic polysaccharide monooxygenase or, ex vivo, electrodes depends on the flexibility of the electron transferring domain and its connecting linker, but the regulatory mechanism is little understood. Studying the linker sequences of currently characterized CDH classes we observed that the inner, mobile linker sequence is flanked by two outer linker regions that are in close contact with the adjacent domain. A function-based definition of the linker region in CDH is proposed and has been verified by rationally designed variants of Neurospora crassa CDH. The effect of linker length and its domain attachment on electron transfer rates has been determined by biochemical and electrochemical methods, while distances between the domains of CDH variants were computed. This study elucidates the regulatory mechanism of the interdomain linker on electron transfer by determining the minimum linker length, observing the effects of elongated linkers, and testing the covalent stabilization of a linker part to the flavodehydrogenase domain. The evolutionary guided, rational design of the interdomain linker provides a strategy to optimize electron transfer rates in multidomain enzymes and maximize their bioelectrocatalytic performance., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

An on-body antenna, comprised of two closely-spaced antiphase patch elements, for microwave imaging may provide enhanced signal penetration into the tissue. By further integrating a 180-degree on-chip power combiner with the dual antiphase patch antenna element, a low-profile miniaturized antenna, integrated into a single 18.5 mm x 10 mm x 1.6 mm circuit board assembly, is designed and evaluated both numerically and experimentally. This is the smallest on-body antenna known to the authors for the given frequency band. This linearly polarized antenna may potentially serve as a building block of a dense antenna array for prospective high-resolution microwave imaging. A 2.4 GHz band was chosen as the design target. The final antenna size was a compromise between the miniaturization, the SNR (Signal-to-Noise Ratio), and the targeted antenna bandwidth (2.3-2.5 GHz). The effect of surface waves (the secondary radiating components) was also factored in the design consideration, while maximizing the detected signals' SNR.

Oil from oilseeds can be extracted by mechanical extraction (pressing), aqueous extraction, or by extraction with organic solvents. Although solvent extraction is the most efficient method, organic solvents are a potential hazard to the life and health for workers as well as to the environment, when solvent vapours are released and act as air pollutant with a high ozone-forming potential. Pressing is safer, environmentally friendly, and it preserves valuable natural components in the resulting oils. The problems associated with pressing are the high energy consumption and the lower yield of oil extraction, because the applied mechanical force does not completely destroy the structural cell components storing the oil. In seed cells, the oil is contained in the form of lipid bodies (oleosomes) that are surrounded by a phospholipid monolayer with a protein layer on the surface. These lipid bodies are further protected by the seed cell walls consisting mainly of polysaccharides such as pectins, hemicelluloses and cellulose, but also of glycoproteins. The use of hydrolases to degrade these barriers is a promising pretreatment strategy to support mechanical extraction and improve the oil yield. It is advisable to use a combination of enzymes with different activities when considering the multicompartment and multicomponent structure of oilseed cells. This article gives an overview of the microstructure and composition of oilseed cells, reviews enzymes capable of destroying oil containing cell compartments, and summarizes the main parameters of enzymatic treatment procedures, such as the composition of the enzyme cocktail, the amount of enzyme and water used, temperature, pH, and the duration of the treatment. Finally, it analyzes the efficiency of proteolytic, cellulolytic and pectolytic enzyme pretreatment to increase the yield of mechanically extracted oil from various types of vegetable raw materials with the main focus on oilseeds., Competing Interests: CONFLICT OF INTEREST The authors declare no conflict of interest.

On-body antennas for use in microwave imaging (MI) systems can direct energy around the body instead of through the body, thus degrading the overall signal-to-noise ratio (SNR) of the system. This work introduces and quantifies the usage of modern metal-backed RF absorbing foam in conjunction with on-body antennas to dampen energy flowing around the body, using both simulations and experiments. A head imaging system is demonstrated herein but the principle can be applied to any part of the body including the torso or extremities. A computational model was simulated numerically using Ansys HFSS. A physical prototype in the form of a helmet with embedded antennas was built to compare simulations with measured data. Simulations and measurements demonstrate that usage of such metal-backed RF-absorbing foams can significantly reduce around-body coupling from Transmit (Tx) and Receive (Rx) antennas by approximately 10dB. Thus, the overall SNR of the MI system can be substantially improved using this low-cost and affordable method.

Enantiomers have the same physical properties but different chemical properties due to the difference in the orientation of groups in space and thus Chiral discrimination is quite necessary, as an enantiomer of drug can have lethal effects. In this study, we used the CC2 cage for chiral discrimination of amino acids using density functional theory. The results indicated the physisorption of amino acids in the central cavity of the cage. Among the four selected amino acids, proline showed maximum interactions with the cage and maximum chiral discrimination energy is also observed in the case of proline that is 2.78 kcal/mol. Quantum theory of atoms in molecules and noncovalent interaction index analyses showed that the S enantiomer in each case has maximum interactions. The charge transfer between the analyte and surface is further studied through natural bond orbital analysis. It showed sensitivity of cage for both enantiomers, but a more pronounced effect is seen for S enantiomers. In frontier molecular orbital analysis, the least E H-L gap is observed in the case of R proline with a maximum charge transfer of -0.24 e - . Electron density difference analysis is carried out to analyze the pattern of the charge distribution. The partial density of state analysis is computed to understand the contribution of each enantiomer in overall density of the complexes. Our results show that S-CC2 porous organic cages have a good ability to differentiate between two enantiomers. S-CC2 porous organic cages efficiently differentiated the S enantiomer from the R enantiomers of selected amino acids.

Attractive interactions between ions of like charge remain an elusive concept. Observing and quantifying this type of interaction in liquids and solutions is still a major challenge. Recently, we have shown that cation-cation interactions are present in hydroxyl-functionalized ionic liquids and that they can be controlled by the shape, charge distribution and functionality of the ions. In the present study, we demonstrate that cationic cluster formation does not only change the local structures of the ionic liquids but also influences the dynamics of the cations in a characteristic way. We show that solid-state 2 H NMR spectroscopy is well suited for the study of molecular motion, even if the hydrogen bonded species of interest are indistinguishable due to fast deuteron exchange. We also provide valuable information about the applicability of well-accepted relaxation models.

Electronic and nonlinear optical properties of endohedral metallofullerenes are presented. The endohedral metallofullerenes contain transition metal encapsulated in inorganic fullerenes X 12 Y 12 (X = B, Al & Y = N, P). The endohedral metallofullerenes ( endo-TM@X 12 Y 12 ) possess quite interesting geometric and electronic properties, which are the function of the nature of the atom and the size of fullerene. NBO charge and frontier molecular orbital analyses reveal that the transition metal encapsulated Al 12 N 12 fullerenes ( endo-TM@Al 12 N 12 ) are true metalides when the transition metals are Ni, Cu and Zn. Endo-Cr@Al 12 N 12 and endo-Co@Al 12 N 12 are at the borderline between metalides and electrides with predominantly electride characteristics. The other members of the series are excess electron systems, which offer interesting electronic and nonlinear optical properties. The diversity of nature possessed by endo-TM@Al 12 N 12 is not prevalent for other fullerenes. Endo-TM@Al 12 P 12 are true metalides when the transition metals are (Cr-Zn). HOMO-LUMO gaps (E H-L ) are reduced significantly for these endohedral metallofullerenes, with a maximum percent decrease in E H-L of up to 70%. Many complexes show odd-even oscillating behavior for E H-L and dipole moments. Odd electron species contain large dipole moments and small E H-L, whereas even electron systems have the opposite behavior. Despite the decrease in E H-L , these systems show high kinetic and thermodynamic stabilities. The encapsulation of transition metals is a highly exergonic process. These endo-TM@X 12 Y 12 possess remarkable nonlinear optical response in which the first hyperpolarizability reaches up to 2.79 × 10 5 au for endo-V@Al 12 N 12 . This study helps in the comparative analysis of the potential nonlinear optical responses of electrides, metalides and other excess electron systems. In general, the potential nonlinear optical response of electrides is higher than metalides but lower than those of simple excess electron compounds. The higher non-linear optical response and interesting electronic characteristics of endo-TM@Al 12 N 12 complexes may be promising contenders for potential NLO applications.

Background: The association of vitiligo with psoriasis is inconsistent in the current literature., Objective: To assess the bidirectional association between vitiligo and psoriasis., Methods: A population-based study was performed to compare vitiligo patients (n = 20,851) with age-, sex- and ethnicity-matched control subjects (n = 102,475) regarding the incidence of new-onset and the prevalence of preexisting psoriasis. Adjusted hazard ratios (HRs) and adjusted odds ratios (ORs) were calculated by cox regression and logistic regression, respectively., Results: The incidence rate of new-onset psoriasis was estimated at 7.9 (95% CI 6.4-9.7) and 4.7 (95% CI 4.1-5.3) cases per 10,000 person-years among patients with vitiligo and controls, respectively. Patients with vitiligo experienced an increased risk of psoriasis (fully-adjusted HR 1.71; 95% CI 1.35-2.17; P < 0.001). On the other hand, the odds of vitiligo were only marginally elevated among patients with preexisting psoriasis (fully-adjusted OR 1.19; 95% CI 1.01-1.40; P = 0.051). Compared to other patients with vitiligo, those with vitiligo and comorbid psoriasis were older at the onset of the disease and had a greater prevalence of metabolic and cardiovascular comorbidities., Conclusions: A diagnosis of vitiligo predisposes individuals to develop subsequent psoriasis. Clinicians managing dermatologic patients ought to be aware of this comorbidity. Further research is required to explicate the pathomechanism underlying this epidemiological observation., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)