Magnetically Induced Binary Ferrocene with Oxidized Iron.

Ferrocene is perhaps the most popular and well-studied organometallic molecule, but our understanding of its structure and electronic properties has not changed for more than 70 years. In particular, all previous attempts of chemically oxidizing pure ferrocene by binding directly to the iron center have been unsuccessful, and no significant change in structure or magnetism has been reported. Using a metal organic framework host material, we were able to fundamentally change the electronic and magnetic structure of ferrocene to take on a never-before observed physically stretched/bent high-spin Fe(II) state, which readily accepts O2 from air, chemically oxidizing the iron from Fe(II) to Fe(III). We also show that the binding of oxygen is reversible through temperature swing experiments. Our analysis is based on combining Mößbauer spectroscopy, extended X-ray absorption fine structure, in situ infrared, SQUID, thermal gravimetric analysis, and energy dispersive X-ray fluorescence spectroscopy measurements with ab initio modeling.

Liposomal versus plain bupivacaine for pain control following vaginal reconstruction.

INTRODUCTION: Liposomal bupivacaine (LB) is a depot formulation of bupivacaine, which releases the drug over 72 hours to prolong local pain control. This retrospective study compares the effect of using LB versus plain bupivacaine on postoperative pain control, length of hospital stay and cost among patients undergoing vaginal reconstructive surgery. MATERIALS AND METHODS: Patients who underwent vaginal reconstructive surgery with levatorplasty and received an injection of 20 cc of either plain bupivacaine or LB for pudendal nerve block were included. The primary outcomes included postoperative narcotic use and subjective pain score. The secondary outcome was postoperative length of stay. Comparisons between groups were performed using the T test, Mann Whitney U and Chi-square tests with p < 0.05 considered significant. RESULTS: Between June 2016 and December 2021, 25 patients had received LB as a pudendal nerve block and 25 had received plain bupivacaine. Demographics between groups were similar. There was no difference between postoperative morphine equivalent dose (MED) for plain bupivacaine versus LB (25.3 ± 65.8 vs. 24.9 ± 31.7 MED; p = 0.159) or length of hospital stay (15.8 ± 12.0 hours vs. 23.8 ± 20.0; p = 0.094). Furthermore, subjective pain was also similar between groups (0 vs. 1.6 ± 2.6, p = 0.68), (4.6 ± 2.3 vs. 4.9 ± 2.0 average POD 1 pain, p = 0.534) and (4.3 ± 2.1 for vs. 4.9 ± 2.1 average POD 2 pain, p = 0.373). CONCLUSION: LB is not superior to plain bupivacaine for controlling pain following vaginal reconstructive surgery, and justification for the exponentially greater cost of LB is not supported. Prospective investigations with larger sample sizes are needed to determine the optimal pain management for levatorplasty in vaginal reconstructive surgery.

Identifying the Gate-Opening Mechanism in the Flexible Metal-Organic Framework UTSA-300.

Atomic-level understanding of the gate-opening phenomenon in flexible porous materials is an important step toward learning how to control, design, and engineer them for applications such as the separation of gases from complex mixtures. Here, we report such mechanistic insight through an in-depth study of the pressure-induced gate-opening phenomenon in our earlier reported metal-organic framework (MOF) Zn(dps)2(SiF6) (dps = 4,4'-dipyridylsulfide), also called UTSA-300, using isotherm and calorimetry measurements, in situ infrared spectroscopy, and ab initio simulations. UTSA-300 is shown to selectively adsorb acetylene (C2H2) over ethylene (C2H4) and ethane (C2H6) and undergoes an abrupt gate-opening phenomenon, making this framework a highly selective gas separator of this complex mixture. The selective adsorption is confirmed by pressure-dependent in situ infrared spectroscopy, which, for the first time, shows the presence of multiple C2H2 species with varying strengths of bonding. A rare energetic feature at the gate-opening condition of the flexible MOF is observed in our differential heat energies, directly measured by calorimetry, showcasing the importance of this tool in adsorption property exploration of flexible frameworks and offering an energetic benchmark for further energy-based fundamental studies. Based on the agreement of this feature with ab initio-based adsorption energies of C2H2 in the closed-pore structure UTSA-300a ("a" refers to the activated form), this feature is assigned to the weakening of the H-bond C-H···F formed between C2H2 and fluorine of the MOF. Our analysis identifies the weakening of this H-bond, the expansion of the closed-pore MOF upon successive C2H2 coadsorption until its volume is close to that of the open-pore MOF, and the spontaneous gate opening to energetically favor C2H2 adsorption in the open-pore structure as crucial steps in the gate-opening mechanism in this system.

Porous Ti-MOF-74 Framework as a Strong-Binding Nitric Oxide Scavenger.

Combining synthesis, infrared spectroscopy, and ab initio modeling we show that the titanium-based porous framework Ti-MOF-74 has potential as an environmental nitric oxide (NO) scavenger, exhibiting an extraordinarily strong binding affinity and selectivity over other flue-gas components. The robustness upon exposure to water vapor and high flue-gas stack temperatures suggests that this material can perform well in an industrial environment. In-depth analysis of the Ti-NO bond indicates that the NO forms a strong covalent bond with the Ti. The process of this NO bond formation involves a reaction with the OH- capping groups of the Ti to form NOx groups, after which the excess NO binds to the open Ti metal sites. Ti-MOF-74 thus becomes, to the best of our knowledge, the first known porous framework that binds NO significantly stronger than water, providing novel avenues for environmental and physiological scavenging applications.

Crystallizing Atomic Xenon in a Flexible MOF to Probe and Understand Its Temperature-Dependent Breathing Behavior and Unusual Gas Adsorption Phenomenon.

Flexible metal-organic frameworks (MOFs) hold great promise as smart materials for specific applications such as gas separation. These materials undergo interesting structural changes in response to guest molecules, which is often associated with unique adsorption behavior not possible for rigid MOFs. Understanding the dynamic behavior of flexible MOFs is crucial yet challenging as it involves weak host-guest interactions and subtle structural transformation not only at the atomic/molecular level but also in a nonsteady state. We report here an in-depth study on the adsorbate- and temperature-dependent adsorption in a flexible MOF by crystallizing atomic gases into its pores. Mn(ina)2 shows an interesting temperature-dependent response toward noble gases. Its nonmonotonic, temperature-dependent adsorption profile results in an uptake maximum at a temperature threshold, a phenomenon that is unusual. Full characterization of Xe-loaded MOF structures is performed by in situ single-crystal and synchrotron X-ray diffraction, IR spectroscopy, and molecular modeling. The X-ray diffraction analysis offers a detailed explanation into the dynamic structural transformation and provides a convincing rationalization of the unique adsorption behavior at the molecular scale. The guest and temperature dependence of the structural breathing gives rise to an intriguing reverse of Xe/Kr adsorption selectivity as a function of temperature. The presented work may provide further understanding of the adsorption behavior of noble gases in flexible MOF structures.

Blending Ionic and Coordinate Bonds in Hybrid Semiconductor Materials: A General Approach toward Robust and Solution-Processable Covalent/Coordinate Network Structures.

Inorganic semiconductor materials are best known for their superior physical properties, as well as their structural rigidity and stability. However, the poor solubility and solution-processability of these covalently bonded network structures has long been a serious drawback that limits their use in many important applications. Here, we present a unique and general approach to synthesize robust, solution-processable, and highly luminescent hybrid materials built on periodic and infinite inorganic modules. Structure analysis confirms that all compounds are composed of one-dimensional anionic chains of copper iodide (CumIm+22-) coordinated to cationic organic ligands via Cu-N bonds. The choice of ligands plays an important role in the coordination mode (µ1-MC or µ2-DC) and Cu-N bond strength. Greatly suppressed nonradiative decay is achieved for the µ2-DC structures. Record high quantum yields of 85% (λex = 360 nm) and 76% (λex = 450 nm) are obtained for an orange-emitting 1D-Cu4I6(L6). Temperature dependent PL measurements suggest that both phosphorescence and thermally activated delayed fluorescence contribute to the emission of these 1D-AIO compounds, and that the extent of nonradiative decay of the µ2-DC structures is much less than that of the µ1-DC structures. More significantly, all compounds are remarkably soluble in polar aprotic solvents, distinctly different from previously reported CuI based hybrid materials made of charge-neutral CumXm (X = Cl, Br, I), which are totally insoluble in all common solvents. The greatly enhanced solubility is a result of incorporation of ionic bonds into extended covalent/coordinate network structures, making it possible to fabricate large scale thin films by solution processes.

Help-seeking behavior among Danish veterans with self-reported mental problems - a 22 years register-based follow-up study.

Purpose: To estimate the prevalence of utilization of mental health services (MHS) among Danish veterans with self-reported deployment-related mental problems and to identify predictors for help-seeking behavior for mental problems among veterans.Materials and methods: Data on deployment characteristics was obtained from a telephone survey in 2011 among a random sample of veterans deployed during 1996-2009. Only respondents reporting sustained or less sustained mental problems were included, and data from national registers on mental health service utilization and prescribed psychotropics covering up to 22 years of follow-up was obtained. Logistic regression analysis was performed to identify predictors of help-seeking.Results: Of 434 respondents with self-reported problems, 333 (77%) received any mental health service after deployment. Of those, 48 (23%) received any help within the first 2 years after deployment start while 128 (61%) did not receive help until after 4 years. Significant predictors for MHS utilization included sustained mental problems, combat exposure characteristics (being injured in combat, watching a fellow soldier suffer injuries), and deployment-related factors (being deployed to >1 mission and being deployed to Afghanistan).Conclusion: These findings highlight the importance of time, and hereunder of a long follow-up period, when measuring the prevalence of help-seeking behavior for individuals experiencing mental problems after military deployment.

Does Early Low-Intensity Aerobic Exercise Hasten Recovery in Adolescents With Sport-Related Concussion?

Clinical Scenario: Low-intensity aerobic exercise (LIAEX) below the threshold of symptom exacerbation has been shown to be superior to rest for resolving prolonged (>4 wk) symptoms following sport-related concussion (SRC), but the effects of LIAEX earlier than 4 weeks after SRC need to be elucidated. Focused Clinical Question: Does LIAEX within the first 4 weeks following SRC hasten symptom resolution? Summary of Key Findings: Two randomized controlled trials (RCT) and 1 nonrandomized trial involving adolescent athletes (10-19 y) were included. One RCT reported faster recovery time with LIAEX versus placebo stretching. Likewise, recovery time was faster with LIAEX versus rest in the nonrandomized trial, but not in the underpowered RCT, although effect sizes were similar between these studies (0.5 and 0.4, respectively). All 3 studies reported a reduction in concussion symptom severity with LIAEX; however, the magnitude of symptom reduction across the recovery timeline was greater in the LIAEX group than the rest group in the nonrandomized trial, but not the 2 RCTs. Importantly, no adverse effects or incidence of delayed recovery from LIAEX were reported in any of the studies. Clinical Bottom Line: LIAEX initiated within 10 days after SRC may facilitate a faster recovery time versus placebo stretching or rest, although additional clinical trials are strongly advised to verify this. Strength of Recommendation: Level 1b and 2b evidence suggests subsymptom exacerbation LIAEX may decrease Postconcussion Symptom Scale scores and hasten symptom resolution in adolescent athletes following SRC.

Thermally Activated Adsorption in Metal-Organic Frameworks with a Temperature-Tunable Diffusion Barrier Layer.

Modification of the external surfaces of metal-organic frameworks offers a new level of control over their adsorption behavior. It was previously shown that capping of MOFs with ethylenediamine (EDA) can effectively retain small gaseous molecules at room temperature. Reported here is a temperature-induced variation in the capping-layer gate-opening mechanism through a combination of in situ infared experiments and ab initio simulations of the capping layer. An atypical acceleration and increase in the loading of weakly adsorbed molecules upon raising the temperature above room temperature is observed. These findings show the discovery of novel temperature-dependent kinetics that goes beyond standard kinetics and suggest a new avenue for tailoring selective adsorption by thermally tuning the surface barrier.

Role of Hydrogen Bonding on Transport of Coadsorbed Gases in Metal-Organic Frameworks Materials.

Coadsorption of multicomponents in metal-organic framework (MOF) materials can lead to a number of cooperative effects, such as modification of adsorption sites or during transport. In this work, we explore the incorporation of NH3 and H2O into MOFs preloaded with small molecules such as CO, CO2, and SO2. We find that NH3 (or H2O) first displaces a certain amount of preadsorbed molecules in the outer portion of MOF crystallites, and then substantially hinders diffusion. Combining in situ spectroscopy with first-principles calculations, we show that hydrogen bonding between NH3 (or H2O) is responsible for an increase of a factor of 7 and 8 in diffusion barrier of CO and CO2 through the MOF channels. Understanding such cooperative effects is important for designing new strategies to enhance adsorption in nanoporous materials.

Modulation of Water Vapor Sorption by a Fourth-Generation Metal-Organic Material with a Rigid Framework and Self-Switching Pores.

Hydrolytically stable adsorbents are needed for water vapor sorption related applications; however, design principles for porous materials with tunable water sorption behavior are not yet established. Here, we report that a platform of fourth-generation metal-organic materials (MOMs) with rigid frameworks and self-switching pores can adapt their pores to modulate water sorption. This platform is based upon the hydrolytically stable material CMOM-3S, which exhibits bnn topology and is composed of rod building blocks based upon S-mandelate ligands, 4,4-bipyridine ligands, and extraframework triflate anions. Isostructural variants of CMOM-3S were prepared using substituted R-mandelate ligands and exhibit diverse water vapor uptakes (20-67 cm3/g) and pore filling pressures ( P/ P0, 0.55-0.75). [Co2( R-4-Cl-man)2(bpy)3](OTf) (33R) is of particular interest because of its unusual isotherm. Insight into the different water sorption properties of the materials studied was gained from analysis of in situ vibrational spectra, which indicate self-switching pores via perturbation of extraframework triflate anions and mandelate linker ligands to generate distinctive water binding sites. Water vapor adsorption was studied using in situ differential spectra that reveal gradual singlet water occupancy followed by aggregation of water clusters in the channels upon increasing pressure. First-principles calculations identified the water binding sites and provide structural insight on how adsorbed water molecules affect the structures and the binding sites. Stronger triflate hydrogen bonding to the framework along with significant charge redistribution were determined for water binding in 33R. This study provides insight into a new class of fourth-generation (self-switching pores) MOM and the resulting effect upon water vapor sorption properties.

Coumarin Triazabutadienes for Fluorescent Labeling of Proteins.

The use of small-molecule fluorophores to label proteins with minimal perturbation in response to an external stimulus is a powerful tool to probe chemical and biochemical environments. Herein, we describe the use of a coumarin-modified triazabutadiene that can deliver aryl diazonium ions to fluorescently label proteins by tyrosine-selective modification. The labeling can be triggered by low-pH-induced liberation of the diazonium species, thus making the fluorophore especially useful in labeling biochemical surroundings such as those found within the late endosome. Additionally, we show that a variety of coumarin triazabutadienes might also be prone to releasing their diazonium cargo after irradiation with UV light.

Quantitative Attachment of Bimetal Combinations of Transition-Metal Ions to the Surface of TiO2 Nanorods.

We report the sequential, quantitative loading of transition-metal ions (Cr3+, Mn2+, Fe2+, Co2+, Ni2+, and Cu2+) onto the surface of rod-shaped anatase TiO2 nanocrystals in bimetallic combinations (6 C2 = 15) to form M,M'-TiO2 nanocrystals. The materials were characterized with transmission electron microscopy (TEM), powder X-ray diffraction (XRD), elemental analysis, X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy. TEM and XRD data indicate that the sequential adsorption of metal ions occurs with the retention of the phase and morphology of the nanocrystal. Atomistic models of the M,M'-TiO2 nanocrystals were optimized with density functional theory calculations. Calculated UV-visible absorption spectra and partial charge density maps of the donor and acceptor states for the electronic transitions indicate the importance of metal-to-metal charge transfer (MMCT) processes.

Evidence for increased behavioral control by punishment in children with attention-deficit hyperactivity disorder.

BACKGROUND: The behavioral sensitivity of children with ADHD to punishment has received limited theoretical and experimental attention. This study evaluated the effects of punishment on the response allocation of children with ADHD and typically developing children. METHOD: Two hundred and ten children, 145 diagnosed with ADHD, completed an operant task in which they chose between playing two simultaneously available games. Reward was arranged symmetrically across the games under concurrent variable interval schedules. Asymmetric punishment schedules were superimposed; responses on one game were punished four times as often as responses on the other. RESULTS: Both groups allocated more of their responses to the less frequently punished alternative. Response bias increased significantly in the ADHD group during later trials, resulting in missed reward trials and reduced earnings. CONCLUSIONS: Punishment exerted greater control over the response allocation of children with ADHD with increased time on task. Children with ADHD appear more sensitive to the cumulative effects of punishment than typically developing children.

Light-Activated Triazabutadienes for the Modification of a Viral Surface.

Chemical crosslinking is a versatile tool for the examination of biochemical interactions, in particular host-pathogen interactions. We report the critical first step toward the goal of probing these interactions by the synthesis and use of a new heterobifunctional crosslinker containing a triazabutadiene scaffold. The triazabutadiene is stable to protein conjugation and liberates a reactive aryl diazonium species upon irradiation with 350 nm light. We highlight the use of this technology by modifying the surface of several proteins, including the dengue virus envelope protein.

Behavioral sensitivity to changing reinforcement contingencies in attention-deficit hyperactivity disorder.

BACKGROUND: Altered sensitivity to positive reinforcement has been hypothesized to contribute to the symptoms of attention-deficit hyperactivity disorder (ADHD). In this study, we evaluated the ability of children with and without ADHD to adapt their behavior to changing reinforcer availability. METHOD: Of one hundred sixty-seven children, 97 diagnosed with ADHD completed a signal-detection task in which correct discriminations between two stimuli were associated with different frequencies of reinforcement. The response alternative associated with the higher rate of reinforcement switched twice during the task without warning. For a subset of participants, this was followed by trials for which no reinforcement was delivered, irrespective of performance. RESULTS: Children in both groups developed an initial bias toward the more frequently reinforced response alternative. When the response alternative associated with the higher rate of reinforcement switched, the children's response allocation (bias) followed suit, but this effect was significantly smaller for children with ADHD. When reinforcement was discontinued, only children in the control group modified their response pattern. CONCLUSIONS: Children with ADHD adjust their behavioral responses to changing reinforcer availability less than typically developing children, when reinforcement is intermittent and the association between an action and its consequences is uncertain. This may explain the difficulty children with ADHD have adapting their behavior to new situations, with different reinforcement contingencies, in daily life.

Causes and Timing of Unplanned ICU Admissions Among Trauma Patients at a Level 1 Trauma Center.

BACKGROUND: Unexpected ICU admissions are a key quality metric in trauma care. The purpose of this study is to identify the most common causes of unplanned ICU admissions among trauma patients at an ACS-verified level 1 trauma center. METHODS: A retrospective review was conducted of all trauma patients with unplanned admission to the ICU at a level 1 trauma center between 2019 and 2021. Unplanned ICU admissions were categorized into (1) "bounce-backs," patients previously admitted to the ICU and (2) "upgrades," patients who had not previously been cared for in the ICU. RESULTS: Of 300 unexpected ICU transfers, bounce-backs accounted for 69% and upgrades 31%. The most common injuries were traumatic brain injuries (40%) and rib fractures (41.3%). In-hospital mortality rate was 10% and did not significantly differ between bounce-backs and upgrades (12 vs 5%, P = .92). Respiratory distress was the most common cause of transfer (41.1%), followed by neurologic (29.6%) and cardiovascular decline (21.2%). Patients were on average 928 mL fluid positive 72 hours prior to transfer (t > 0, P < .0001), and 295 mL fluid positive in the 24 hours prior to transfer (t > 0, P .0003). Patients transferred for respiratory distress were no more fluid over-balanced than those transferred for other reasons. CONCLUSION: We found a large percent of unplanned transfers occurring within 48 hours of admission or transfer out of the ICU suggesting under-triage as a leading cause of bounce-backs and upgrades. Respiratory distress was the leading cause of transfer. These findings highlight opportunities for targeted interventions.

Remote triage practices in general surgery patients from freestanding emergency departments: A 6-year analysis.

BACKGROUND: Freestanding emergency departments have risen in popularity as a means to expand access to care. Although some evaluation of freestanding emergency department utility in specific patient populations exists, management of surgical patients via remote triage and disposition has not been previously described. We report our experience with remote triage to discharge home, level I trauma center, or community hospital admission for general surgery patients who present to an affiliated freestanding emergency department. METHODS: A retrospective cohort study of patients presenting to freestanding emergency departments requiring surgical consultation between 2016 and 2021 was conducted. Outcomes included disposition, length of stay, surgical intervention, 30-day mortality, and readmission. Undertriage and overtriage rates were calculated and defined as the following: (1) discharge undertriage-discharge home with 30-day emergency department visit/readmission; 2) transfer undertriage-transfers to community hospital requiring transfer to trauma center; and (3) overtriage-admissions <24 hours without surgery. RESULTS: Of 1,105 patients, 15% were discharged home, 27% were transferred to trauma centers, and 58% were transferred to community hospitals. Patients admitted to trauma centers were older and had higher acuity pathology, whereas patients admitted to community hospitals had higher operative rates with shorter lengths of stay, operating room time, 30-day readmission, and mortality. Transfer undertriage was 0.9% (n = 6), with only 1 patient requiring transfer from a community hospital to a trauma center for disease acuity. Discharge undertriage was 12% (n = 20) due to worsening or persistent pathology. Overtriage was 5.5% (n = 52), with most having a partial small bowel obstruction or ambiguous diagnostic imaging requiring observation. CONCLUSION: Remote surgery triage at freestanding emergency departments, without an in-person examination, demonstrated both low undertriage and overtriage rates, reflecting appropriate triage practices.

Level III Trauma Centers Achieve Comparable Outcomes in Blunt Splenic Injury as Level I Centers.

INTRODUCTION: Identifying patients who can be safely managed in lower-level trauma centers is critical to avoid overburdening level I centers. This study examines the transfer patterns and outcomes of blunt splenic injury (BSI) patients cared for at 2 regional level III trauma centers as compared to an associated level I center. METHODS: A retrospective cohort study was conducted including all trauma patients with BSI admitted to 2 level III trauma centers (TC3) and a level I center (TC1) between 2012 and 2022. Patients were broken into 3 categories: TC1, TC3, and transfer patients (transferred from TC3 to TC1). RESULTS: A total of 1480 patients were admitted to TC1, 208 patients to TC3, and 128 were transferred. 22.7% of transfer patients were children. No difference in splenic injury grade was seen between patients managed at TC1 and TC3. Patients presenting to TC1 had more severe concomitant injuries. Patients underwent urgent splenectomy at similar rates at TC1 and TC3 (15.1 vs 18.7%, P = .1). Successful nonoperative management was achieved at similar rates (81.3 vs 75.5%, P = .1). When controlling for ISS and ED disposition, there was no significant difference in length of stay (LOS), ICU LOS, and inpatient mortality between TC1 and TC3. CONCLUSION: Level III centers effectively managed BSI achieving comparable outcomes to the level 1 center. Transfers commonly occurred in pediatric and multisystem trauma patients, though high-grade splenic injuries were not predictive of transfer. High-grade BSI can be safely managed at level III centers without need for transfer.

Extracorporeal Membrane Oxygenation During Surgical Stabilization of Rib Fractures in Successful Management of Severe Blunt Chest Trauma.

Early surgical stabilization of rib fracture (SSRF) improves outcomes in patients with flail physiology and severely displaced fractures. We present two cases of patients with severe chest injury and large flail segment who underwent SSRF while on veno-venous extracorporeal membrane oxygenation (VV-ECMO). The patients developed respiratory failure within 24 hours of admission requiring VV-ECMO. The extent of their chest wall injury limited pulmonary mechanics prohibiting transition off VV-ECMO. Therefore, SSRF was performed on hospital days 2 and 3 and while on VV-ECMO support. Stabilizing the chest wall allowed for improved ventilation and successful decannulation from VV-ECMO on postoperative days 3 and 4. Ultimately, both achieved a functional recovery and were discharged home. These cases demonstrate a unique thoracic damage control strategy wherein SSRF is performed while on VV-ECMO. Improving chest stability and pulmonary mechanics with SSRF allowed for safe transition off VV-ECMO and achieved a favorable long-term outcome.