The effect of ancillary ligands on hydrocarbon C-H bond functionalization by uranyl photocatalysts.

The aqueous uranyl dication has long been known to facilitate the UV light-induced decomposition of aqueous VOCs (volatile organic compounds), via the long-lived highly efficient, uranyl excited state. The lower-energy visible light excited uranyl ion is also able to cleave unactivated hydrocarbon C-H bonds, yet the development of this reactivity into controlled and catalytic C-H bond functionalization is still in its infancy, with almost all studies still focused on uranyl nitrate as the precatalyst. Here, hydrocarbon-soluble uranyl nitrate and chloride complexes supported by substituted phenanthroline (Ph2phen) ligands are compared to each other, and to the parent salts, as photocatalysts for the functionalization of cyclooctane by H atom abstraction. Analysis of the absorption and emission spectra, and emission lifetimes of Ph2phen-coordinated uranyl complexes demonstrate the utility of the ligand in light absorption in the photocatalysis, which is related to the energy and kinetic decay profile of the uranyl photoexcited state. Density functional theory computational analysis of the C-H activation steps in the reaction show how a set of dispersion forces between the hydrocarbon substrate and the Ph2phen ligand provide control over the H atom abstraction, and provide predictions of selectivity of H atom abstraction by the uranyl oxo of the ring C-H over the ethyl C-H in an ethylcyclohexane substrate.

Phosphatidylinositol (4,5)-bisphosphate drives the formation of EGFR and EphA2 complexes.

Receptor tyrosine kinases (RTKs) regulate many cellular functions and are important targets in pharmaceutical development, particularly in cancer treatment. EGFR and EphA2 are two key RTKs that are associated with oncogenic phenotypes. Several studies have reported functional interplay between these receptors, but the mechanism of interaction is still unresolved. Here we utilize a time-resolved fluorescence spectroscopy called PIE-FCCS to resolve EGFR and EphA2 interactions in live cells. We tested the role of ligands and found that EGF, but not ephrin A1 (EA1), stimulated hetero-multimerization between the receptors. To determine the effect of anionic lipids, we targeted phospholipase C (PLC) activity to alter the abundance of phosphatidylinositol (4,5)-bisphosphate (PIP 2 ). We found that higher PIP 2 levels increased homo-multimerization of both EGFR and EphA2, as well as hetero-multimerization. This study provides a direct characterization of EGFR and EphA2 interactions in live cells and shows that PIP 2 can have a substantial effect on the spatial organization of RTKs.

Defining Overweight and Obesity by Percent Body Fat instead of Body Mass Index.

OBJECTIVE: Thresholds for overweight and obesity are currently defined by body mass index (BMI), a poor surrogate marker of actual adiposity (percent body fat, %BF). Practical modern technologies provide estimates of %BF but medical providers need outcome-based %BF thresholds to guide patients. This analysis determines %BF thresholds based on key obesity-related comorbidities, exhibited as metabolic syndrome (MetSyn). These limits were compared to existing BMI thresholds of overweight and obesity. DESIGN: Correlational analysis of data from cross sectional sampling of 16,918 adults (8,734 men and 8,184 women) from the US population, accessed by the National Health and Nutrition Examination Survey (NHANES) public use datasets. RESULTS: Individuals measured by BMI as overweight (BMI>25 kg/m2) and with obesity (BMI>30 kg/m2) included 5% and 35% of individuals with MetSyn, respectively. For men, there were no cases of MetSyn below 18%BF, %BF equivalence to "overweight" (i.e., 5% of MetSyn individuals) occurred at 25%BF, and "obesity" (i.e., 35% of MetSyn individuals) corresponded to 30%BF. For women, there were no cases of MetSyn below 30%BF, "overweight" occurred at 36%BF, and "obesity" corresponded to 42%BF. Comparison of BMI to %BF illustrates the wide range of variability in BMI prediction of %BF, highlighting the potential importance of using more direct measures of adiposity to manage obesity-related disease. CONCLUSIONS: Practical methods of body composition estimation can now replace the indirect BMI assessment for obesity management, using threshold values provided from this study. Clinically relevant "overweight" can be defined as 25 and 36% BF for men and women, respectively, and "obesity" is defined as 30 and 42% BF for men and women.

Effect of sensor number and location on accelerometry-based vertical ground reaction force estimation during walking.

Knee osteoarthritis is a major cause of global disability and is a major cost for the healthcare system. Lower extremity loading is a determinant of knee osteoarthritis onset and progression; however, technology that assists rehabilitative clinicians in optimizing key metrics of lower extremity loading is significantly limited. The peak vertical component of the ground reaction force (vGRF) in the first 50% of stance is highly associated with biological and patient-reported outcomes linked to knee osteoarthritis symptoms. Monitoring and maintaining typical vGRF profiles may support healthy gait biomechanics and joint tissue loading to prevent the onset and progression of knee osteoarthritis. Yet, the optimal number of sensors and sensor placements for predicting accurate vGRF from accelerometry remains unknown. Our goals were to: 1) determine how many sensors and what sensor locations yielded the most accurate vGRF loading peak estimates during walking; and 2) characterize how prescribing different loading conditions affected vGRF loading peak estimates. We asked 20 young adult participants to wear 5 accelerometers on their waist, shanks, and feet and walk on a force-instrumented treadmill during control and targeted biofeedback conditions prompting 5% underloading and overloading vGRFs. We trained and tested machine learning models to estimate vGRF from the various sensor accelerometer inputs and identified which combinations were most accurate. We found that a neural network using one accelerometer at the waist yielded the most accurate loading peak vGRF estimates during walking, with average errors of 4.4% body weight. The waist-only configuration was able to distinguish between control and overloading conditions prescribed using biofeedback, matching measured vGRF outcomes. Including foot or shank acceleration signals in the model reduced accuracy, particularly for the overloading condition. Our results suggest that a system designed to monitor changes in walking vGRF or to deploy targeted biofeedback may only need a single accelerometer located at the waist for healthy participants.

Flax fibre reinforced alginate poloxamer hydrogel: assessment of mechanical and 4D printing potential.

The mechanical and printing performance of a new biomaterial, flax fibre-reinforced alginate-poloxamer based hydrogel, for load-bearing and 4D printing biomedical applications is described in this study. The-self suspendable ability of the material was evaluated by optimising the printing parameters and conducting a collapse test. 1% of the flax fibre weight fraction was sufficient to obtain an optimum hydrogel composite from a mechanical perspective. The collapse test showed that the addition of flax fibres allowed a consistent print without support over longer distances (8 and 10 mm) than the unreinforced hydrogel. The addition of 1% of flax fibres increased the viscosity by 39% and 129% at strain rates of 1 rad s-1 and 5 rad s-1, respectively, compared to the unreinforced hydrogel. The distributions of fibre size and orientation inside the material were also evaluated to identify the internal morphology of the material. The difference of coefficients of moisture expansion between the printing direction (1.29 × 10-1) and the transverse direction (6.03 × 10-1) showed potential for hygromorphic actuation in 4D printing. The actuation authority was demonstrated by printing a [0°; 90°] stacking sequence and rosette-like structures, which were then actuated using humidity gradients. Adding fibres to the hydrogel improved the repeatability of the actuation, while lowering the actuation authority from 0.11 mm-1 to 0.08 mm-1. Overall, this study highlighted the structural and actuation-related benefits of adding flax fibres to hydrogels.

Double Ventricular Response with Aberrant Conduction Leading to Ventricular Dysfunction.

Double ventricular response (DVR), where a single P wave results in two QRS complexes, is a rare presentation of dual AV node physiology. It has been associated with ventricular dysfunction in the setting of incessant tachycardia. We present the case of an otherwise healthy adolescent who had frequent DVR without tachycardia leading to left ventricular dysfunction. Slow pathway modification led to a significant reduction in ectopy and normalization of ventricular function. This highlights that DVR without tachycardia might lead to ventricular dysfunction in pediatric patients. Slow pathway modification with reduction of ectopy may be sufficient to restore ventricular function.

Comprehensive Studies of Adsorption Equilibrium and Kinetics for Selected Aromatic Organic Compounds on Activated Carbon.

This work presents a comprehensive analysis of the adsorption of selected aromatic organic compounds on activated carbons. Both the equilibrium and kinetics of adsorption were studied using UV-Vis spectrophotometry. The influence of a number of factors: pH, contact time, presence of an accompanying substance, adsorbate concentration, as well as the mass and size of adsorbent grains, on the adsorption process from aqueous solutions was investigated. Phenol, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol and methylene blue (as an accompanying substance) were selected as adsorbates. GAC 1240W and RIAA activated carbons were used as adsorbents. The equilibrium data were analyzed using the generalized Langmuir isotherm equation (R2 = 0.912-0.996). Adsorption rate data were fitted using a multi-exponential kinetic equation (1 - R2 = (1.0 × 10-6)-(8.2 × 10-4)). As an additional parameter, the half-time was also used to present the influence of selected factors on the adsorption kinetics. An increase in the amount of adsorption was demonstrated with increasing contact time as well as with decreasing solution pH and adsorbent grain size. For selected systems, an increase in the adsorption rate was observed with increasing adsorbate concentration, adsorbent mass and at lower pH values. In some cases, the presence of an accompanying substance also resulted in an increase in adsorption kinetics. In the tested experimental systems, optimal conditions for adsorption were established (T = 298 K, pH = 2, contact time: 7 days, grain diameter: >0.5 mm and the ratio of the mass of the adsorbent to the volume of the adsorbate solution: 1 g/L). Additionally, the acid-base properties (potentiometric titration), morphology (SEM) and structure (TEM) of the used adsorbents were also examined.

Rates and Risk Factors for 30-Day Morbidity After One-Stage Vertical Banded Gastroplasty Conversions: A Retrospective Analysis.

Background: The vertical banded gastroplasty (VBG) is a historic restrictive bariatric operation often requiring further surgery. In this investigation utilizing the 2021 Metabolic and Bariatric Surgery Accreditation and Quality Improvement Program (MBSAQIP) national dataset, we aim to better define the outcomes of VBG conversions.Methods: We queried the 2021 MBSAQIP dataset for patients who underwent a conversion from a VBG to Roux-en-Y gastric bypass (RYGB) or sleeve gastrectomy (SG). Demographics, comorbidities, laboratory values, and additional patient factors were examined. Rates of key consequential outcome measures 30-day readmission, reoperation, reintervention, mortality, and a composite endpoint (at least 1 of the 4) were further calculated.Results: We identified 231 patients who underwent conversion from VBG to SG (n = 23), RYGB (n = 208), or other anatomy (n = 6), of which 93% of patients were female, and 22% of non-white race. The median age was 56 years and body-mass index (BMI) was 43 kg/m2. The most common surgical indications included weight considerations (48%), reflux (25%), anatomic causes (eg, stricture, fistula, and ulcer; 10%), and dysphagia (6.5%). Thirty-day morbidity rates included reoperation (7.8%), readmission (9.1%), reintervention (4.3%), mortality (.4%), and the composite endpoint (15%). Upon bivariate analysis, we did not identify any specific risk factor for the 30-day composite endpoint.Discussion: One-stage VBG conversions to traditional bariatric anatomy are beset with higher 30-day morbidity relative to primary procedures. Additional MBSAQIP data will be required for aggregation, to better characterize the risk factors inherent in these operations.

Light-Triggered Inflation of Microdroplets.

Driven systems composed largely of droplets and fuel make up a significant portion of microbiological function. At the micrometer scale, fully synthetic systems that perform an array of tasks within a uniform bulk are much more rare. In this work, we introduce an innovative design for solid-in-oil composite microdroplets. These microdroplets are engineered to nucleate an internal phase, undergo inflation, and eventually burst, all powered by a steady and uniform energy input. We show that by altering the background input, volumetric change and burst time can be tuned. When the inflated droplets release the inner contents, colloidal particles are shown to transiently attract to the release point. Lastly, we show that the system has the ability to perform multiple inflation-burst cycles. We anticipate that our conceptual design of internally powered microdroplets will catalyze further research into autonomous systems capable of intricate communication as well as inspire the development of advanced, responsive materials.

Specific connectivity optimizes learning in thalamocortical loops.

Thalamocortical loops have a central role in cognition and motor control, but precisely how they contribute to these processes is unclear. Recent studies showing evidence of plasticity in thalamocortical synapses indicate a role for the thalamus in shaping cortical dynamics through learning. Since signals undergo a compression from the cortex to the thalamus, we hypothesized that the computational role of the thalamus depends critically on the structure of corticothalamic connectivity. To test this, we identified the optimal corticothalamic structure that promotes biologically plausible learning in thalamocortical synapses. We found that corticothalamic projections specialized to communicate an efference copy of the cortical output benefit motor control, while communicating the modes of highest variance is optimal for working memory tasks. We analyzed neural recordings from mice performing grasping and delayed discrimination tasks and found corticothalamic communication consistent with these predictions. These results suggest that the thalamus orchestrates cortical dynamics in a functionally precise manner through structured connectivity.

The Oligomeric State of Vasorin in the Plasma Membrane Measured Non-Invasively by Quantitative Fluorescence Fluctuation Spectroscopy.

Vasorin (VASN), a transmembrane protein heavily expressed in endothelial cells, has garnered recent interest due to its key role in vascular development and pathology. The oligomeric state of VASN is a crucial piece of knowledge given that receptor clustering is a frequent regulatory mechanism in downstream signaling activation and amplification. However, documentation of VASN oligomerization is currently absent. In this brief report, we describe the measurement of VASN oligomerization in its native membranous environment, leveraging a class of fluorescence fluctuation spectroscopy. Our investigation revealed that the majority of VASN resides in a monomeric state, while a minority of VASN forms homodimers in the cellular membrane. This result raises the intriguing possibility that ligand-independent clustering of VASN may play a role in transforming growth factor signaling.

The Modified Reactive Strength Index Is a Valid Measure of Lower-Body Explosiveness in Male and Female High School Athletes.

ABSTRACT: Witte, BC, Schouten, TC, Westphal, JA, VanZile, AW, Jones, DD, Widenhoefer, TL, Dobbs, WC, Jagim, AR, Luedke, JA, and Almonroeder, TG. The modified reactive strength index is a valid measure of lower-body explosiveness in male and female high school athletes. J Strength Cond Res XX(X): 000-000, 2024-The modified reactive strength index (mRSI) is a commonly used metric to quantify lower-body explosiveness during countermovement jump (CMJ) performance. However, few studies have attempted to examine its validity as a measure of explosiveness, particularly among high school athletes. The purpose of this study was to examine the validity of the mRSI as a measure of lower-body explosiveness among a relatively large sample of male and female high school athletes from various sports. As part of this study, male (n = 132) and female (n = 43) high school athletes performed CMJs, while ground reaction forces were recorded using a force platform. The vertical ground reaction force data collected during the CMJs were used to derive the following variables: peak force (PF), peak power, time to PF, time to take-off, peak rate of force development, and the mRSI. Principal component analysis was applied and reduced these variables into 2 components related to "force" and "speed." The mRSI loaded on both the force (loading = 0.82) and speed (loading = -0.46) components, indicating that it incorporates elements of both force and speed, although it loaded more strongly on the force component than the speed component. The observed pattern of cross-loading suggests that the mRSI is generally a valid measure of lower-body explosiveness for male and female high school athletes.

I was like sh*t this is gonna hurt': Implementing Self-Sampling of Dried Blood Spots to Measure HIV Viral Load.

Background: Sexual minority men (SMM) with HIV who use stimulants may experience greater difficulties with antiretroviral therapy adherence which amplifies risk for unsuppressed HIV viral load (VL). Remote monitoring of VL could support efforts to rapidly respond to sub-optimal adherence. Methods: This qualitative study enrolled 24 SMM with HIV who use stimulants to examine experiences with two different dried blood spots (DBS) self-sampling devices (i.e., Tasso-M20 vs. HemaSpot HD) to measure VL. Participants were asked to complete self-sampling of DBS using both devices, and then participated in a 45-minute semi-structured interview. Interviews focused on ease of use, device preference, experiences with receiving and mailing kits, and barriers to participating in research. A thematic analysis was conducted to analyze interviews transcripts. Results: Twenty-two participants (92%) returned the Tasso-M20 and 21 (88%) returned the Hemaspot HD devices. Among the 22 participants that completed qualitative interviews, twenty-three codes were identified and collapsed within seven themes. Preferences for devices were based on convenience, pain and prior experiences with finger-pricking technology. Participants emphasized that clearer instructions with contingency plans for self-sampling of DBS would improve the user experience with self-sampling of DBS. Intersectional stigma (e.g., HIV, sexual minority status, and substance use) was noted as an important consideration in implementing self-sampling of DBS. Promoting decision making, or the option to choose sampling method based on personal preferences, may improve engagement and likelihood of DBS completion. Conclusions: Findings will guide the broader implementation of self-sampling of DBS to optimize VL monitoring in SMM with HIV who use stimulants.

Occurrence, Predictors, and Management of Late Vascular Complications following Extracorporeal Membrane Oxygenation.

BACKGROUND: Vascular complications (VC) associated with Extracorporeal Membrane Oxygenation (ECMO) during index hospitalization are prevalent and associated with increased mortality. Few studies have evaluated late VC following ECMO; this study aims to assess occurrence and management practices of late VC following discharge. METHODS: A retrospective single-institution review was performed of all patients surviving initial hospitalization after being cannulated for central or peripheral veno-venous (VV) or veno-arterial (VA) ECMO between January 1st 2019 and December 31st 2020. Primary outcomes were to categorize and determine the rate late VC. Late VCs were defined as any cannulated vessel injury resulting from ECMO cannulation presenting after discharge from index hospitalization. Analysis was conducted by cannulated vessel and stratified by VV or VA ECMO configurations. RESULTS: A total of 229 patients were identified, of which 50.6% (n=116) survived until discharge. Late VC occurred in 7.8% of the surviving cohort (n=9/116); with a median time until presentation of 150 days (IQR 83-251). The most common late VC was infection (n=5, 55.6%) followed by progression to limb threatening ischemia (n=4, 44.4%). Urgent procedures were required in 55.6% of patients (n=5), while 44.4% (n=4) were elective interventions. Interventions performed for management of late VC included lower extremity arterial revascularization (n=6, 66.7%), major (n=1, 11.1%) or minor amputation (n=1, 11.1%), and wound debridement (n=1, 11.1%). The majority of patients presenting with late VC had initially been cannulated for peripheral-VA ECMO (n=8, 88.9%) and 1 patient (11.1%) was cannulated for peripheral-VV ECMO. VC during index hospitalization were seen in 77.8% (n=7) of patients returning with late VC. Odds for late VC were significantly increased in patients that had been cannulated for ECMO as part of extracorporeal-cardio-pulmonary resuscitation (E-CPR) (OR 8.4, p=0.016) and in cases were patient had experienced an index VC during index hospitalization (OR 19.3, p=0.001). CONCLUSION: Late vascular complications after peripheral ECMO cannulation are not rare, particularly after arterial cannulation. Patients should be followed closely early after surviving ECMO with wound evaluation and formal assessment of perfusion with ankle-branchial indices in the cannulated limb.

Feline Forensics: Revealing the Unique Decomposition of Cats.

Limited data about the differences between the decomposition of animals with fur exist within the forensic veterinary medicine discipline. Due to the sheer number of animals used as animal models and the number of animals that exist, determining stages of decomposition that are applicable for all species is difficult. Typically, assessing what stage of decomposition a decedent is in is subjective due to the visual assessment of decomposition changes. A method developed to rectify this issue was the total body score (TBS) method, which assigns a numerical value based on the degree of decomposition to the head, torso, and limbs. The purpose of this study was to examine the decomposition of cats, identify any unique decomposition characteristics, and determine the rate of decomposition using total body score and accumulated degree days (ADDs). Twelve domestic short-haired cats were placed in a grassy field in West Lafayette, IN. An assessment of TBS was documented for each cat and each experimental group. An exponential relationship between TBS and ADD was documented. Overall, there was not a significant difference in the rate of decomposition or total body scores between the groups (Z = -91.00, p = 0.0672).

Prospective randomized pilot trial comparing prophylactic vs therapeutic cerebrospinal fluid drainage during complex endovascular thoracoabdominal aortic aneurysm repair.

BACKGROUND: Endovascular techniques have transformed the management of thoracoabdominal aortic aneurysms (TAAAs). However, spinal cord ischemia (SCI) remains a prevalent and devastating complication. Prophylactic drainage of cerebrospinal fluid (CSF) is among the proposed strategies for prevention of SCI. Although prophylactic CSF drainage is widely used and conceptually attractive, prophylactic CSF drains have not been demonstrated to definitively prevent the occurrence nor mitigate the severity of SCI in endovascular TAAA repair. Whether or not outcomes of prophylactic drains are superior to therapeutic drains remains unknown. This pilot study was performed to determine the feasibility of a randomized clinical trial designed to investigate the role of prophylactic vs therapeutic CSF drains in the prevention of SCI in patients undergoing endovascular TAAA repair using branched and fenestrated endovascular aortic repair (FBEVAR). METHODS: This was a prospective multicenter randomized pilot clinical trial conducted at The University of Alabama at Birmingham and The University of Massachusetts. Twenty patients were enrolled and randomized to either the prophylactic drainage or therapeutic drainage groups, prior to undergoing FBEVAR for extensive TAAAs and arch aortic aneurysms. This was a pilot feasibility study that was not powered to detect statistical differences in clinical outcomes. The primary outcome was feasibility of randomization and compliance with a shared lumbar drain protocol. Secondary outcomes included rate of drain complications and SCI. RESULTS: Twenty patients were enrolled and successfully randomized, without any crossovers, to either the control cohort (n = 10), without prophylactic drains, or the experimental cohort (n = 10), with prophylactic drains. There were no differences in age, comorbidities, or history of prior aortic surgery across the cohorts. All patients were treated with FBEVAR. Aneurysm classifications were as follows: Extent I (10%), Extent II (50%), Extent III (35%), and Extent IV (5%). The average length of aortic coverage was 207 ± 21.6 mm. The length of aortic coverage did not vary across cohorts, nor did procedural times or blood loss volume. Compliance with the SCI prevention protocol was 100% across both groups. Within the prophylactic drain cohort, one patient experienced an adverse event related to lumbar drain placement, manifested as an epidural hematoma requiring laminectomy, without neurologic deficit (n = 1/10; 10%). There was one SCI event (n = 1/20; 5%), which occurred in the prophylactic drain cohort on postoperative day 9 following an episode of hypotension related to a gastrointestinal bleed. CONCLUSIONS: The role of prophylactic CSF drains for the prevention of SCI following endovascular TAAA repair is a topic of ongoing research, with many current practices based on expert opinion and experience, rather than rigorous scientific data. This study demonstrates the feasibility of a multicenter randomized clinical trial to evaluate the role of prophylactic vs therapeutic CSF drains in the prevention of SCI in patients undergoing endovascular TAAA repair.

Observation of WWγ Production and Search for Hγ Production in Proton-Proton Collisions at sqrt[s]=13 TeV.

The observation of WWγ production in proton-proton collisions at a center-of-mass energy of 13 TeV with an integrated luminosity of 138 fb^{-1} is presented. The observed (expected) significance is 5.6 (5.1) standard deviations. Events are selected by requiring exactly two leptons (one electron and one muon) of opposite charge, moderate missing transverse momentum, and a photon. The measured fiducial cross section for WWγ is 5.9±0.8(stat)±0.8(syst)±0.7(modeling) fb, in agreement with the next-to-leading order quantum chromodynamics prediction. The analysis is extended with a search for the associated production of the Higgs boson and a photon, which is generated by a coupling of the Higgs boson to light quarks. The result is used to constrain the Higgs boson couplings to light quarks.