High State Research Articles

Metal–Organic Frameworks with Axial Cobalt–Oxygen Coordination Modulate Polysulfide Redox for Lithium–Sulfur Batteries

AbstractAlthough the ultrahigh theoretical energy density and cost‐effectiveness, lithium–sulfur (Li‐S) batteries suffer from sluggish conversion kinetics and the shuttling effect of soluble lithium polysulfides (LiPSs). Herein, conductive hexagonal cobalt‐organic framework (Co‐HTP) nanosheets are anchored in situ on carboxyl graphene (CG) substrates and serve as host catalysts to modulate the polysulfide redox. Substantial characterizations identify that the local coordination environment of the quadrilateral Co–N4 units transforms into an asymmetric penta‐coordinated O–Co–N4 with axial Co─O coordination, which triggers spin polarization and remarkable electron delocalization of Co 3d orbital. The higher spin state and lower local electron density of the O–Co–N4 sites induce more active electronic states in Co‐HTP/CG and facilitate orbital hybridization with polysulfides to form more stable bond orders. Such optimized electronic structure significantly accelerates redox kinetics and enhances the adsorption strength of polysulfides. These merit the lithium–sulfur battery based on Co‐HTP/CG with a high reversible capacity, impressive rate capability, and prolonged cycling performance over 500 cycles. This work will enrich the design philosophy of modulating the spintronic structure of electrocatalysts for advanced Li–S batteries and beyond.

Vacancy engineering-induced spin polarization in heterogeneous phosphides by simple iron salt infiltration for efficient overall water splitting

Optimizing electronic structure and facilitating electron transfer modulation in electrocatalyst is the key to enhancing overall water splitting (OWS) performance. In this work, the heterogeneous transition metal phosphide Fe-CoPv/Ni2P@NF, consisting of cobalt phosphide and nickel phosphide, is obtained by simple iron salt infiltration and high-temperature phosphatisation. Due to the doping of iron-atom and the formation of phosphorus vacancies, the activity of metal atoms with higher valence states and spins is induced, and then highly active Fe/Co-O-Ni channels are generated in the dynamic water-splitting process, thereby increasing the exposure of reaction center and total electron transfer rate. The catalytic mechanism is attributed to reducing the potential barrier of phase remodeling and optimizing the intermediate binding strength, thus thoroughly stimulating OER and HER activities. The Fe-CoPv/Ni2P@NF shows superior performance, requiring only total voltages of 1.626 V (OWS) to reach 100 mA·cm−2 and maintaining ultra-high stability for 500 h, suggesting promising industrial applications.

Chronic pelvic pain syndrome in women of reproductive age: An observational cohort clinical ultrasound study

Background. The annual number of new cases of chronic pelvic pain syndrome in women of reproductive age is increasing worldwide. The high prevalence of this condition among the able-bodied female population leads to higher state expenditures on the treatment of this category of patients. New methods of diagnosis and early prophylaxis contribute to reducing economic burden associated with chronic pelvic pain syndrome in women and improving health of the female population as a fundamental demographic factor.Objectives. To determine somatic, obstetric-gynecological, anatomical, and psycho-emotional predictors of chronic pelvic pain syndrome.Methods. An observational cohort clinical and ultrasound study involved 60 patients of reproductive age. The study was conducted on the basis of the clinic for women, Voronezh City Outpatient Clinic No. 1 — clinical base of the Department of Obstetrics and Gynecology No. 2, Voronezh State Medical University named after N. N. Burdenko, Russia. According to clinical and laboratory data, the participants were divided into 2 groups. Group 1 (n = 30) included women of reproductive age without clinical manifestations of chronic pelvic pain syndrome; Group 2 (n = 30) enrolled women of reproductive age clinically diagnosed with chronic pelvic pain.Results. The mean age of the study participants in the main group comprised 27.4 ± 6.30 and 26.3 ± 7.25 years in the control group, p > 0.05. Diseases of gastrointestinal tract, endocrine, cardiovascular, musculoskeletal and urinary systems, as well as neurocirculatory and vegetative disorders prevailed in the structure of somatic pathology in the main group, p < 0.001. Analysis of obstetric and gynecologic anamnesis revealed no statistically significant differences in the incidence of gynecologic pathology in the study groups. However, according to the detailed analysis of the delivery history of the participants, 23 patients of the main group (76 %) and 3 patients (6.6 %) of the control group underwent episiotomy during labor, p < 0.001. The evaluation of the comparison groups in terms of pain component in myofascial syndrome involved the pain rating index, number of selected descriptors, sensory index of the selected descriptors, emotional index of the selected descriptors, and pain intensity. Statistically significant differences were revealed for all of the above indicators, thereby confirming a reliable picture of pathopsychological changes in the compared groups of women. The analysis of the ultrasound parameters of topographic and anatomical relationships demonstrated the relevant change in the following parameters: urethral length, diameter of the external urethral sphincter, angle between the external urethra and the body of the bladder, direct and transverse dimensions of the levator hiatus in the studied groups under the muscle tension.Conclusion. An issue of early diagnosis and prophylaxis of chronic pelvic pain syndrome in women of reproductive age remains urgent and requires interdisciplinary participation of medical specialists. The development of new approaches to ultrasound evaluation of pelvic floor will increase the effectiveness of therapeutic and prophylactic measures and reduce the economic burden of this nosology in the morbidity structure of the able-bodied female population.

Effect of N2-H2 remote plasma nitridation temperature on surface properties of Te-doped GaSb crystals

GaSb is regarded as one of the most promising near-infrared optoelectronic materials in recent years. However, due to the ease of natural oxidation of GaSb, the surface will promptly form a thick oxide layer which is highly resistant to removal, resulting in detrimental interface defects and higher surface state density. Although studies have demonstrated the feasibility of plasma for removing oxide, the ultra-high vacuum is necessary for complete removal, which poses challenges for commercial applications. Herein, we optimized the nitrogen plasma passivation process for Te-doped GaSb, combining remote plasma source with Atomic Layer Deposition (ALD) in-situ annealing to modify GaSb (001) surface, which approaches non-damaging treatment. The temperature during passivation will affect nitrogenation on GaSb surface, result in enrichment of metallic Sb when reaching 573 K, and impact emission efficiency. By setting the passivation temperature at 523 K and combining with in-situ annealing, the photoluminescence (PL) efficiency of GaSb has doubled. This demonstrates the validity of low-temperature nitrogen passivation in improving surface state and reducing defect density on GaSb.

Birthing consciousness and the flow experience during physiological childbirth

ProblemIt has been demonstrated that birth without medical intervention conveys significant physical and psychological benefits to the mother and her newborn baby. However, there is a need to include women's subjective experience of physiological birth to understand and promote it. BackgroundThe theoretical concept of “birthing consciousness” hypothesizes that women during natural childbirth sometimes experience a specific altered state of consciousness, which is a positive peak experience that resembles “flow” in many aspects. AimTo investigate the underexplored connection between the physiological mode of childbirth and altered states of consciousness during childbirth. MethodsIsraeli women with childbirth experience were recruited through social media (Facebook groups with a focus on childbirth and motherhood). Participants (n = 766) completed an online survey: the Flow State Scale (FSS) and a demographic questionnaire. FindingsDifferences were found between modes of birth as to flow state, as women who experienced physiological childbirth (i.e., with no epidural anesthesia or instrumental interventions) had a higher flow state during birth. DiscussionThis link empirically confirms the phenomenon of birthing consciousness. All nine dimensions of the mental state of flow apply to childbirth: challenge-skill balance, action-awareness merging, clear goals, unambiguous feedback, concentration on the task, sense of control, loss of self-consciousness, transformation of time, and autotelic experience. ConclusionUnderstanding a women's subjective experience during physiological birth can enhance clinical understanding of physiological birth thus promoting positive physiological birth experiences – which has crucial health benefits. We propose that more studies need to be done to promote experiencing flow during physiological birth.

A theoretical study on excited-state dynamical properties and laser cooling of zinc monohydride including spin-orbit couplings.

By means of highly accurate ab initio and dynamical calculations, we identify a suitable laser cooling candidate that contains a transition metal element, namely zinc monohydride (ZnH). The internally contracted multireference configuration interaction method is employed to compute the five lowest-lying Λ-S states of ZnH with the spin-orbit coupling effects included, and very good agreement is obtained between our calculated and experimental spectroscopic data. Our findings show that the position of crossing point of the A2Π and B2Σ+ states of ZnH is above the v' = 2 vibrational level of the A2Π state indicating that the crossings with higher electronic states will have no effect on laser cooling. Hence, we construct a feasible laser-cooling scheme for ZnH using five lasers based on the A2Π1/2 → X2Σ+ 1/2 transition, which features a large vibrational branching ratio R 00 (0.8458), a large number of scattered photons (9.8 × 103) and an extremely short radiative lifetime (64ns). The present work demonstrates the importance of electronic state crossings and spin-orbit couplings in the study of molecular laser cooling.

The fiscal function of the customs authorities of Ukraine in the conditions of the legal regime of martial state: analysis of the problems in the context of the decisions of the higher government bodies

The article analyzes the problems of implementation of the fiscal function by Ukrainian customs authorities during the legal regime of martial law in the context of the decisions of higher state authorities. The significance of the fiscal function of the customs authorities of Ukraine for filling the revenue part of the State Budget of Ukraine in the pre-war period and after the beginning of the full-scale invasion of the russian troops on the territory of Ukraine was researched. The approach to reforming the customs authorities of Ukraine based on the priority of the fiscal function is critically evaluated. The necessity of using modern trends in the organization and functioning of customs administrations in the developed countries of the world during reforms of the Ukrainian customs authorities is indicated, which primarily consist in changing approaches to understanding the activities of customs authorities of Ukraine not only as fiscal, but also as protective and regulatory. In the course of the analysis of the normative legal acts of the government and the parliament, adopted with the aim of stabilizing the situation in the economy of Ukraine after the beginning of the full-scale invasion of the russian troops on the territory of Ukraine, a number of shortcomings of the rule-making activities of these higher state authorities were revealed, which led to the failure of the state budget to receive significant amounts of customs payments. Based on the study of the norms of acts of the Verkhovna Rada of Ukraine and the Cabinet of Ministers of Ukraine, changes to the relevant normative legal acts were proposed, which could improve the state of implementation of the fiscal function of the customs authorities of Ukraine in the first weeks after the introduction of martial law on the territory of Ukraine. It has been established the need to involve employees of specialized units of the State Customs Service of Ukraine in the development of normative legal acts that affect the implementation of the fiscal function by the customs authorities of Ukraine. It is indicated the basic directions of improvement of the regulatory and legal regulation of the activity of the customs in the implementation of their fiscal function.

Comparative study of microstructure and mechanical properties of cold rolled and annealed CoCrFeNi-MEA and CoCrFeNiMn-HEA fabricated by laser energy deposition

Equi-atomic quaternary CoCrFeNi Medium-entropy alloy (MEA) and quinary CoCrFeNiMn high-entropy alloy (HEA) are fabricated by laser energy deposition, followed by 5-pass cold rolling to total reduction of 70 % and annealing at temperatures of 600–1000 °C for 1 h. CoCrFeNi-MEA is severely cracked while CoCrFeNiMn- HEA is slightly cracked after cold rolling. Hardness of as deposited and fully recrystallized (heat treating temperature at 800–1000 °C) CoCrFeNi-MEAs are slightly higher than those of CoCrFeNiMn- HEAs, due to the larger atomic size misfit and lattice strain in CoCrFeNi-MEA than in CoCrFeNiMn-HEA. However, the higher microhardness of CoCrFeNiMn-HEAas-rolled than CoCrFeNi-MEAas-rolled is associated with the higher strain state in CoCrFeNiMn-HEAas-rolled than in CoCrFeNi-MEAas-rolled. With the increase of heat-treating temperature, microhardness of CoCrFeNi-MEA increases first and then decreases due to the precipitation hardening effect of Cr-rich (B2) particles in CoCrFeNi-MEAR-600. Microhardness of CoCrFeNiMn-HEA decreases with the increase of annealing temperature because of the weaker precipitation hardening effect of MnNi phase (L10) and Cr-rich particles (BCC) after annealing at 600 ℃ and higher temperatures. CoCrFeNi-MEAR-700 is much harder than CoCrFeNiMn-HEAR-700 because CoCrFeNi-MEAR-700 is partially recrystallized and CoCrFeNiMn-HEAR-700 is fully recrystallized. Strength behavior of the two alloys is consistent with microhardness behavior. {100}<110> texture component is acquired in both CoCrFeNi-MEAas-rolled and CoCrFeNiMn-HEAas-rolled. <111>//ND texture is observed in both alloys after annealing at 600 ℃. Orientation of recrystallized grains is random in both alloys. Size of recrystallized grains in CoCrFeNiMn-HEA is slightly larger than those in CoCrFeNi-MEA since homologous temperature (T/Tm) of CoCrFeNiMn-HEA is slightly higher than that of CoCrFeNi-MEA.

Isomeric Effects of Au28(S-c-C6H11)20 Nanoclusters on Photoluminescence: Roles of Electron-Vibration Coupling and Higher Triplet State.

The exploration of near-infrared photoluminescence (PL) from atomically precise nanoclusters is currently a prominent area of interest owing to its importance in both fundamental research and diverse applications. In this work, we investigate the near-infrared (NIR) photoluminescence mechanisms of two structural isomers of atomically precise gold nanoclusters of 28 atoms protected by cyclohexanethiolate (CHT) ligands, i.e., Au28i(CHT)20 and Au28ii(CHT)20. Based on their structures, analysis of 3O2 (triplet oxygen) quenching of the nanocluster triplet states, temperature-dependent photophysical studies, and theoretical calculations, we have elucidated the intricate processes governing the photoluminescence of these isomeric nanoclusters. For Au28i(CHT)20, its emission characteristics are identified as phosphorescence plus thermally activated delayed fluorescence (TADF) with a PL quantum yield (PLQY) of 0.3% in dichloromethane under ambient conditions. In contrast, the Au28ii(CHT)20 isomer exhibits exclusive phosphorescence with a PLQY of 3.7% in dichloromethane under ambient conditions. Theoretical simulations reveal a larger singlet (S1)-triplet (T1) gap in Au28ii than that in Au28i, and the higher T2 state plays a critical role in both isomers' photophysical processes. The insights derived from this investigation not only contribute to a more profound comprehension of the fundamental principles underlying the photoluminescence of atomically precise gold nanoclusters but also provide avenues for tailoring their optical properties for diverse applications.

Effect of Terminal Phosphate Groups on Collisional Dissociation of RNA Oligonucleotide Anions.

The increasing need for mass spectrometric analysis of RNA molecules calls for a better understanding of their gas-phase fragmentation behaviors. In this study, we investigate the effect of terminal phosphate groups on the fragmentation spectra of RNA oligonucleotides (oligos) using high-resolution mass spectrometry (MS). Negative-ion mode collision-induced dissociation (CID) and higher-energy collisional dissociation (HCD) were carried out on RNA oligos containing a terminal phosphate group on either end, both ends, or neither end. We find that terminal phosphate groups affect the fragmentation behavior of RNA oligos in a way that is dependent on the precursor charge state and the oligo length. Specifically, for precursor ions of RNA oligos of the same sequence, those with 5'- or 3'-phosphate, or both, have a higher charge state distribution and lose the phosphate group(s) in the form of a neutral (H3PO4 or HPO3) or an anion ([H2PO4]- or [PO3]-) upon CID or HCD. Such a neutral or charged loss is most conspicuous for precursor ions of an intermediate charge state, e.g., 3- for 4-nt oligos or 4- and 5- for 8-nt oligos. This decreases the intensity of sequencing ions (a-, a-B, b-, c-, d-, w-, x-, y-, z-ions) and hence is unfavorable for sequencing by CID or HCD. Removal of terminal phosphate groups by calf intestinal alkaline phosphatase improved MS analysis of RNA oligos. Additionally, the intensity of a fragment ion at m/z 158.925, which we identified as a dehydrated pyrophosphate anion ([HP2O6]-), is markedly increased by the presence of a terminal phosphate group. These findings expand the knowledge base necessary for software development for MS analysis of RNA.

Multi-omics landscapes reveal heterogeneity in long COVID patients characterized with enhanced neutrophil activity

BackgroundOmicron variant impacts populations with its rapid contagiousness, and part of patients suffered from persistent symptoms termed as long COVID. The molecular and immune mechanisms of this currently dominant global variant leading to long COVID remain unclear, due to long COVID heterogeneity across populations.MethodsWe recruited 66 participants in total, 22 out of 66 were healthy control without COVID-19 infection history, and 22 complaining about long COVID symptoms 6 months after first infection of Omicron, referred as long COVID (LC) Group. The left ones were defined as non-long COVID (NLC) Group. We profiled them via plasma neutralizing antibody titer, SARS-CoV-2 viral load, transcriptomic and proteomics screening, and machine learning.ResultsNo serum residual SARS-CoV-2 was observed in the participants 6 months post COVID-19 infection. No significant difference in neutralizing antibody titers was found between the long COVID (LC) Group and the non-long COVID (NLC) Group. Transcriptomic and proteomic profiling allow the stratification of long COVID into neutrophil function upregulated (NU-LC) and downregulated types (ND-LC). The NU-LC, identifiable through a refined set of 5 blood gene markers (ABCA13, CEACAM6, CRISP3, CTSG and BPI), displays evidence of relatively higher neutrophil counts and function of degranulation than the ND-LC at 6 months after infection, while recovered at 12 months post COVID-19.ConclusionThe transcriptomic and proteomic profiling revealed heterogeneity among long COVID patients. We discovered a subgroup of long COVID population characterized by neutrophil activation, which might associate with the development of psychiatric symptoms and indicate a higher inflammatory state. Meanwhile, a cluster of 5 genes was manually curated as the most potent discriminators of NU-LC from long COVID population. This study can serve as a foundational exploration of the heterogeneity in the pathogenesis of long COVID and assist in therapeutic targeting and detailed epidemiological investigation of long COVID.

(Invited) Efficient Ternary Nicuw Hydrogen Oxidation Catalysts for Anion Exchange Membrane Fuel Cells

Anion exchange membrane fuel cells (AEMFCs) offer prospective approaches to replace proton exchange membrane fuel cells via cost-effective catalysts and membranes. While significant progress has been made in efficient nonnoble electrocatalysts for oxygen reduction reaction in alkaline media, the hydrogen oxidation reaction (HOR) in the alkaline condition still relies on high platinum loadings to compensate for its sluggish kinetics. Therefore, developing efficient non-noble metal electrocatalysts with Pt-like HOR performances in alkaline electrolytes is highly desired but a great challenge.The hydrogen binding energy (HBE) has been identified as the primary descriptor for the HOR. Additionally, an unfavorable hydroxide binding energy (OHBE) is considered the rate-determining step in the Volmer reaction to generate water. Therefore, an ideal catalyst for HOR should achieve a balance between HBE and OHBE. However, despite being a promising non-noble metal, nickel exhibits excessively high HBE and lacks active sites for hydroxide adsorption, which hinders its further application in the real fuel cell.In this work, NiW was successfully deposited onto Cu to form a ternary Ni-Cu-W alloy catalyst by a chemical reduction method. Through XPS spectra, we found the charge transfer from Ni to W to give Ni a higher valence state, contributing to a weakened hydrogen binding energy. Electrochemical measurements observed Ni-Cu-W exhibit an kinetic activity with 117.9 mA/mgNi at η= 50 mV, which is the highest among the reported platinum group metal-free catalysts. Ni-Cu-W alloy showcased robust stability, with no activity degradation during an accelerated long-term durability test between a low overpotential (-0.1 ~ 0.1 V, vs RHE) with 10,000 cyclic voltammetry scans and only a 5.7% activity loss at η= 50 mV when applying more larger overpotential (-0.1 ~ 0.2 V) with the same cycles. When assembled with this catalyst as anode and Pt/C as cathode, it delivered a peak power density of 289 mW/cm2. Both experimental and theoretical studies were conducted to gain insights into the catalyst's enhanced performance. Our findings revealed that the incorporation of Cu into the catalyst significantly weakened the adsorption of hydrogen species, while simultaneously lowering the energy barrier required for the absorption of hydroxide ions. These key observations might shed light on the underlying mechanisms responsible for the catalyst's improved activity and stability.

(Invited) Delayed Fluorescence from Inverted Singlet and Triplet Excited States

Hund’s multiplicity rule states that for a given electronic configuration, a higher spin state has a lower energy. Rephrasing this rule for molecular excited states predicts a positive energy gap between singlet and triplet excited states (∆E ST). Although there is general agreement that ∆E ST must be positive, the potential for negative ∆E ST in phenalene analogues, such as cycl[3.3.3]azine and heptazine has been discussed during the last two decades.1–4 In this presentation, we report a fluorescent heptazine analogue HzTFEX2 that disobeys Hund’s rule, possessing negative ∆E ST of –11 meV (Fig. 1).5 The energy inversion of the singlet and triplet excited states results in delayed fluorescence with short time constants of 0.2 μs, which anomalously decrease with decreasing temperature due to the emissive singlet character of the lowest-energy excited state. Organic light-emitting diodes using this molecule exhibit a fast transient electroluminescence decay with a maximum external quantum efficiency of 17%, demonstrating potential implications for optoelectronic devices.(1) W. Leupin, J. Wirz, J. Am. Chem. Soc. 102, 6068–6075 (1980).(2) W. Leupin, D. Magde, G. Persy, J. Wirz, J. Am. Chem. Soc. 108, 17–22 (1986).(3) J. Ehrmaier, E. J. Rabe, S. R. Pristash, K. L. Corp, C. W. Schlenker, A. L. Sobolewski, W. Domcke, J. Phys. Chem. A 123, 8099–8108 (2019).(4) P. de Silva, J. Phys. Chem. Lett. 10, 5674–5679 (2019).(5) N. Aizawa, Y.-J. Pu, Y. Harabuchi, A. Nihonyanagi, R. Ibuka, H. Inuzuka, B. Dhara, Y. Koyama, K. Nakayama, S. Maeda, F. Araoka, D. Miyajima, Nature 609, 502 (2022). Figure 1

Modeling the Impact of Microstructure Variation on Charging Capability in Lithium-Ion Batteries

Battery models can be used to predict conditions ripe for lithium metal plating in the anode during rapid charging. One common procedure is to simulate a rapid charge using a pseudo-two-dimensional (P2D) model and determine if and when the minimum local potential reaches 0.0 V with respect to metallic lithium in the anode. This normally occurs at higher states of charge during a DC fast charging or rapid regenerative charging event. However, we have recently determined that three-dimensional (3D) models, while broadly agreeing with P2D results, demonstrate much variation in the in-plane and through plane direction, which P2D models cannot resolve. Because P2D models employ effective medium approximations, any “local” value in the P2D space along the through-plane coordinate represents an average across a slice of the domain. Therefore, it may be insufficient to use minimum anode potentials from P2D models as indicators of local plating and may only be representative of global lithium plating onset.The results of rapid-charge 3D microstructure simulations are compared to P2D results. This allows us to verify whether rapid charging induces negative local potentials at the anode active material surface that are left undetected in a P2D model. The expected result implies that the 3D microstructure model is necessary to predict the onset of lithium plating. We then extend our previous study to look at the impact of design changes on the microstructure performance, and then link the microstructure performance changes to performance metrics at the battery cell, module, pack, and vehicle level. Finally, the impact of variation in the microstructure domain considering particle size variation is quantified to understand tolerances that may be necessary when developing charging schemes.

Bound-state evolution of Dirichlet waveguide with Neumann window(s) in transverse electric fields

The influence of electric field E on a straight Dirichlet waveguide with Neumann window(s) of arbitrary length L is studied theoretically for 2D and 3D geometries. The energy spectrum for the corresponding bound states was obtained and their dependence on E was analysed. At low E , the boundary of the window(s) influenced the properties of the particle contrary to the high E case, where the energies and localization of particle were seen similar in all the geometries. The critical lengths L cr , at which higher excited state emerges into the continuum, at different E were found and their behavior was explained qualitatively. It was found that at high E , the critical lengths of Dirichlet-Neumann boundary window approach the Neumann-Neumann boundary window. This is due to the increase in the fundamental propagation threshold of transverse modes in the wall and window region. On the other hand, the Neumann-Dirichlet boundary window showed an opposite behavior. Furthermore, the polarization of ground state was obtained for different geometries. It was proved that at small L, the polarization reduces to its 1D case. A mathematical treatment and semi classical explanation was provided. Comparative analysis of the 2D and 3D geometries reveals their qualitative similarity and quantitative differences.

The effect of low-dose ketamine on electroencephalographic spectrum during gynecology surgery under desflurane anesthesia.

The perioperative administration of low-dose ketamine has shown potential in postoperative pain management, opioid sparing, and enhancing pain control. This study aimed to investigate the impact of low-dose ketamine on processed electroencephalography (EEG) signals during anesthesia. Forty patients with American Society of Anesthesiologists physical status I-II undergoing elective gynecological surgery were enrolled. EEG monitoring was initiated upon induction of anesthesia. Anesthesia was maintained with desflurane and alfentanil immediately after induction. Fifteen minutes after induction, the ketamine group received a 0.3 mg/kg bolus followed by 0.05 mg/kg/h infusion until completion of surgery. The control group received equivalent saline. Postoperative assessments included pain score (visual analog scale), morphine usage, and quality of recovery. The ketamine group had significantly higher Patient State Index (PSi) values at 10, 20, and 30 minutes after ketamine administration compared to the controls. Ketamine administration led to significant alterations in EEG patterns, including reduced relative power in delta and theta frequency bands, and increased relative power in beta and gamma frequency bands at 10 minutes post-administration. Relative power in the alpha frequency band significantly decreased at 10, 20, and 30 minutes post-administration. However, there were no differences in intraoperative alfentanil consumption, postoperative morphine usage, and pain scores between the two groups. Low-dose ketamine administration during desflurane anesthesia led to notable changes in EEG patterns and PSi values. These findings provide valuable insights into the impact of ketamine on brain activity, and offer essential information for clinical anesthesiologists.

Vibrational relaxation of HOD by collisions with Ar atoms.

Vibrational relaxation of HOD(v12, v3) molecules by collisions with Ar was studied at 298K (v12 denotes coupled bending, v2, and OD stretching, v1, vibrational modes and v3 denotes OH stretching mode). The vibrationally excited HOD molecules were generated by exothermic abstraction reactions of OD radicals with 13 different RH reactants and observed by infrared emission from a fast-flow reactor as a function of Ar pressure and reaction time. State-specific relaxation rate constants were obtained by comparison of the time evolution of the experimental vibrational distributions with numerical kinetic calculations for vibrational populations. The relaxation mechanism was based on the relaxation scheme of H2O studied earlier with the addition of specific channels for HOD(v12, v3). Unlike H2O, energy in stretching and bending vibrations of HOD cannot be separated due to close ν1 and 2ν2 energies, which leads to fast collisional equilibration between these Fermi-resonant levels. For relaxation of the only pure bending state (10), a rate constant of (1.5 ± 0.3) × 10-13cm3molecule-1s-1 was obtained. The relaxation rate of higher v12 states linearly increases with quantum number and very likely includes transfer of population from OD stretch levels, v1, to a lower energy bend level. The average rate constants for the loss of population from (01), (02), and (03) stretching states are (1.1 ± 0.3) × 10-14, (3.2 ± 1.0) × 10-14, and (5.6 ± 1.2) × 10-14cm3molecule-1s-1, respectively.

Effects of Internal, External, and Neutral Attentional Allocation on Post-Event Processing in Social Anxiety

Abstract Purpose Excessive attentional allocation towards threats has been theorized to play a maintaining role in social anxiety disorder (SAD). However, it is unclear if both heightened attentional focus towards internal threats (i.e., interoceptive signals of anxiety) and external threats (i.e., negative social-evaluative cues) are pathogenic. Further, evidence for the causal pathways by which biased attention maintains SAD is limited. The present study tested the effects of experimentally induced internally and externally oriented attention towards threats relative to a neutral control on state anxiety and post-event processing (PEP) in a highly socially anxious sample. Methods During an impromptu speech task, participants (N = 123) were randomized to allocating their attention to their own thoughts, actions, or body sensations (internal condition; n = 41), to an audience member’s reactions and evaluations (external condition; n = 42), or to a neutral object (control condition; n = 40). State anxiety and PEP were assessed immediately following the speech and 24 h later. Results Although no differences between the control condition and the external and internal conditions were observed, participants in the internal condition reported significantly higher state anxiety immediately after the speech and higher PEP 24 h later compared to the external condition. State anxiety immediately after the speech mediated heightened PEP 24 h later among the internal condition compared to the external condition. Conclusions Findings support the theorized maladaptive role of self-focused attention in the maintenance of SAD and suggest that attending internally may be more harmful than attending externally, despite the presence of socio-evaluative threats in the environment.

Early warning signals for bifurcations embedded in high dimensions

Recent work has highlighted the utility of methods for early warning signal detection in dynamic systems approaching critical tipping thresholds. Often these tipping points resemble local bifurcations, whose low dimensional dynamics can play out on a manifold embedded in a much higher dimensional state space. In many cases of practical relevance, the form of this embedding is poorly understood or entirely unknown. This paper explores how measurement of the critical phenomena that generically precede such bifurcations can be used to make inferences about some properties of their embeddings, and, conversely, how prior knowledge about the mechanism of bifurcation can robustify predictions of an oncoming tipping event. These modes of analysis are first demonstrated on a simple fluid flow system undergoing a Hopf bifurcation. The same approach is then applied to data associated with the West African monsoon shift, with results corroborated by existing models of the same system. This example highlights the effectiveness of the methodology even when applied to complex climate data, and demonstrates how a well-resolved spatial structure associated with the onset of atmospheric instability can be inferred purely from time series measurements.

Experimental evidence that activewear retail imagery elicits physiological, attentional and self-reported markers of body image threat in women

Online apparel retail imagery is a prominent threat to women’s body image, particularly segments such as activewear which emphasize the value of women’s bodies. In a within-subjects experiment, we exposed women (N = 128) to imagery randomly selected from activewear, casualwear and homewares websites and measured their gaze behavior, physiological arousal, as well as subjective emotional states and body image ratings. Exposure to activewear retail imagery elicited significantly lower body image ratings, a higher negative emotional state, and a lower positive emotional state compared to the other website imagery conditions. Physiological arousal was significantly higher for both apparel imagery conditions compared to the homewares imagery condition. Body biased gaze behavior was significantly higher for the activewear imagery condition compared to the casualwear imagery condition. Notably, body shame moderated the self-reported but not the physiological experimental effects, such that women with higher body shame experienced stronger adverse changes in their body image and emotional state ratings following activewear exposure. Correlations revealed that self-reported experimental responses to activewear imagery were strongly associated with self-objectification, appearance comparison, disordered eating and body image coping attitudes. Thus, exposure to popular apparel may play a role in maintaining maladaptive body image attitudes and behaviors in women.