Identification, Characterization, and Electronic Structures of Interconvertible Cobalt-Oxygen TAML Intermediates.

The reaction of Li[(TAML)CoIII]·3H2O (TAML = tetraamido macrocyclic tetraanionic ligand) with iodosylbenzene at 253 K in acetone in the presence of redox-innocent metal ions (Sc(OTf)3 and Y(OTf)3) or triflic acid affords a blue species 1, which is converted reversibly to a green species 2 upon cooling to 193 K. The electronic structures of 1 and 2 have been determined by combining advanced spectroscopic techniques (X-band electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), X-ray absorption spectroscopy/extended X-ray absorption fine structure (XAS/EXAFS), and magnetic circular dichroism (MCD)) with ab initio theoretical studies. Complex 1 is best represented as an S = 1/2 [(Sol)(TAML•+)CoIII---OH(LA)]- species (LA = Lewis/Brønsted acid and Sol = solvent), where an S = 1 Co(III) center is antiferromagnetically coupled to S = 1/2 TAML•+, which represents a one-electron oxidized TAML ligand. In contrast, complex 2, also with an S = 1/2 ground state, is found to be multiconfigurational with contributions of both the resonance forms [(H-TAML)CoIV═O(LA)]- and [(H-TAML•+)CoIII═O(LA)]-; H-TAML and H-TAML•+ represent the protonated forms of TAML and TAML•+ ligands, respectively. Thus, the interconversion of 1 and 2 is associated with a LA-associated tautomerization event, whereby H+ shifts from the terminal -OH group to TAML•+ with the concomitant formation of a terminal cobalt-oxo species possessing both singlet (SCo = 0) Co(III) and doublet (SCo = 1/2) Co(IV) characters. The reactivities of 1 and 2 at different temperatures have been investigated in oxygen atom transfer (OAT) and hydrogen atom transfer (HAT) reactions to compare the activation enthalpies and entropies of 1 and 2.

Tissue specific tumor-gene link prediction through sampling based GNN using a heterogeneous network.

A tissue sample is a valuable resource for understanding a patient's symptoms and health status in relation to tumor growth. Recent research seeks to establish a connection between tissue-specific tumor samples and genetic markers (genes). This breakthrough has paved the way for personalized cancer therapies. With this motivation, the proposed model constructs a heterogeneous network based on tumor sample-gene relation data and gene-gene interaction data. This network also incorporates tissue-specific gene expression and primary site-based gene counts as features, enabling tissue-specific predictions. Graph neural networks (GNNs) have proven effective in modeling complex interactions and predicting links within this network. The proposed model has successfully predicted tumor-gene associations by leveraging sampling-based GNNs and link layer embedding. The model's performance metrics, such as AUC-ROC scores, reached approximately 94%, demonstrating the potential of this heterogeneous network in predicting tissue-specific tumor sample-gene links. This paper's findings highlight the importance of tissue-specific associations in cancer research.

Association between preablation and postablation neutrophil-lymphocyte ratio and atrial fibrillation recurrence: A meta-analysis.

Atrial fibrillation (AF) recurrence has become common in patients who have undergone catheter ablation. High neutrophil lymphocyte ratios (NLR) have been linked to an increased risk of recurrent AF. The research is, however, not conclusive. This meta-analysis addressed the value of easily accessible and affordable pre- and postablation NLR levels as indicators of AF recurrence in patients who had undergone ablation. We searched PubMed, SCOPUS, and Google Scholar for pertinent studies through May 2023. Using random effects models, the aggregated odds ratio (OR) of pre- and post-NLR and AF recurrence was estimated. Inter-study heterogeneity was described using I 2 statistics and leave-one-out sensitivity analysis. A p-value < .05 was considered statistically significant. The literature search yielded 270 studies, seven of which were included in this meta-analysis of 1923 patients who experienced AF recurrence after undergoing ablation. There are five retrospective and two prospective studies with a mean follow-up of 20.5 months. The unadjusted odds ratio (OR) of AF recurrence for preablation NLR was 1.33 (95% CI: 1.04-1.71, p < .01, I 2 = 95.49%), while the adjusted OR was 1.45 (95% CI: 0.87-2.43, p < .01, I 2 = 95.1%). The unadjusted odds ratio (OR) for postablation NLR was 1.21 (95% CI: 1.09-1.36, p < .01, I 2 = 85.9%), and the adjusted odds ratio (OR) was 1.28 (95% CI: 0.93-1.76), demonstrating significant heterogeneity (I 2 = 95.32%) with a p-value < .01. NLR was significantly associated with AF recurrence prediction. To detect AF recurrence, we recommend that clinicians add a simple NLR blood test to their diagnostic modalities.

Dysphagia in a Patient With Lewy Body Dementia and Incidental Anterior Cervical Osteophyte: A Case Report.

One of the common problems affecting the elderly is dysphagia, which can be brought on by several things, including the presence of anterior cervical osteophytes. In this case study, a patient with Lewy body dementia is shown to have a case of dysphagia. The patient's primary complaint was dysphagia, which prompted questions regarding the development of underlying Lewy body dementia combined with gradual cognitive deterioration and motor control problems. An upper GI endoscopy was conducted during the patient's hospitalization after a barium swallow suggested esophageal obstruction but found no internal obstruction or any other abnormalities. Following the endoscopic procedure, the patient complained of neck aches. An anterior cervical osteophyte was subsequently discovered by computed tomography, which may have been the primary cause of the patient's dysphagia. The importance of considering coexisting medical conditions in elderly individuals, as well as the significance of promptly assessing and diagnosing dysphagia in the presence of neurodegenerative disorders such as Lewy body dementia, is emphasized by this example.

A Guide to Tris(4-Substituted)-triphenylmethyl Radicals.

Triphenylmethyl (trityl, Ph3C•) radicals have been considered the prototypical carbon-centered radical since their discovery in 1900. Tris(4-substituted)-trityls [(4-R-Ph)3C•] have since been used in many ways due to their stability, persistence, and spectroscopic activity. Despite their widespread use, existing synthetic routes toward tris(4-substituted)-trityl radicals are not reproducible and often lead to impure materials. We report here robust syntheses of six electronically varied (4-RPh)3C•, where R = NMe2, OCH3, tBu, Ph, Cl, and CF3. The characterization reported for the radicals and related compounds includes five X-ray crystal structures, electrochemical potentials, and optical spectra. Each radical is best accessed using a stepwise approach from the trityl halide, (RPh)3CCl or (RPh)3CBr, by controllably removing the halide with subsequent 1e- reduction of the trityl cation, (RPh)3C+. These syntheses afford consistently crystalline trityl radicals of high purity for further studies.

TGF-ß Ligand Cross-Subfamily Interactions in the Response of Caenorhabditis elegans to Bacterial Pathogens.

The Transforming Growth Factor beta (TGF-ß) family consists of numerous secreted peptide growth factors that play significant roles in cell function, tissue patterning, and organismal homeostasis, including wound repair and immunity. Typically studied as homodimers, these ligands have the potential to diversify their functions through ligand interactions that are synergistic, cooperative, additive, and/or antagonistic. In the nematode Caenorhabditis elegans, there are only five TGF-ß ligands, providing an opportunity to dissect ligand interactions in fewer combinations than in vertebrates. As in vertebrates, these ligands can be divided into bone morphogenetic protein (BMP) and TGF-ß/Activin subfamilies that predominantly signal through discrete signaling pathways. The BMP subfamily ligand DBL-1 has been well studied for its role in the innate immune response in C. elegans. Here we show that all five TGF-ß ligands play a role in the immune response. We also demonstrate that multiple TGF-ß ligands act cooperatively as part of this response. We show that the two BMP-like ligands - DBL-1 and TIG-2 - function independently of each other in the immune response, while TIG-2/BMP and the TGF-ß/Activin-like ligand TIG-3 function cooperatively. Structural modeling supports the potential for TIG-2 and TIG-3 to form heterodimers. Finally, we show that canonical DBL-1/BMP receptor and Smad signal transducers function in the response to bacterial pathogens, while components of the DAF-7 TGF-ß/Activin signaling pathway do not play a role in survival. These results demonstrate a novel potential for BMP and TGF-ß/Activin subfamily ligands to interact, and may provide a mechanism for distinguishing the developmental and homeostatic functions of these ligands from an acute response such as the innate immune response to bacterial pathogens.

Elemental and Chemical Phase Analyses of Ras-Family Ayurvedic Medicinal Products.

Fifteen Ayurvedic medicines of Ras-family (herbo-mineral-metallic preparations) from three reputed manufactures were analysed for elemental quantification and their chemical phase identification using the energy-dispersive (ED) and wavelength-dispersive (WD) X-ray fluorescence (XRF) techniques, and powder X-ray diffraction (XRD) technique, respectively. The low-Z elements C, H, N, S and O constituting a major portion of these medicines were also determined by CHNSO analyser and further used as input for XRF analyses. The elements of concern, Hg, Pb and As, are identified in different medicine products with disquiet concentration values (maximum concentration values range ~ 4-10%) and that too with substantial variations in the products from different manufacturers. These elements are identified mainly in the cinnabar (α-HgS)/metacinnabar (ß-HgS), litharge (PbO) and alacranite (As4S4) phases in different medicines. Keeping in view the high concentration of chemicals of the Hg, Pb and As elements in the Ras-family medicines, it is vitally required to investigate their bioaccessibility and surmise the associated toxicological aspects. It is suggested that the formation of the bioaccessible toxic chemical forms of the Hg, Pb and As elements be avoided during preparation of the mineral ingredients or these soluble chemical forms be removed at suitable stage of the preparation. In view of large variations observed for the Hg, Pb and As based ingredients in the Ras family Ayurvedic medicine products from different manufacturers, adequate quality control mechanisms and production regulations are recommended.

Does Moses technology improve the efficiency and outcomes of standard holmium laser lithotripsy? A systematic review and meta-analysis.

Introduction: Retrograde ureteroscopy with holmium laser lithotripsy (HLL) is a standard treatment for urolithiasis. Moses technology has been shown to improve fragmentation efficiency in vitro; however, it is still unclear how it performs clinically compared to standard HLL. We performed a systematic review and meta-analysis evaluating the differences in efficiency and outcomes between Moses mode and standard HLL. Material and methods: We searched the MEDLINE, EMBASE, and CENTRAL databases for randomized clinical trials and cohort studies comparing Moses mode and standard HLL in adults with urolithiasis. Outcomes of interest included operative (operation, fragmentation, and lasing times; total energy used; and ablation speed) and perioperative parameters (stone-free rate and overall complication rate). Results: The search identified six studies eligible for analysis. Compared to standard HLL, Moses was associated with significantly shorter average lasing time (mean difference [MD] -0.95, 95% confidence interval [CI] -1.22 to -0.69 minutes), faster stone ablation speed (MD 30.45, 95% CI 11.56-49.33 mm3/min), and higher energy used (MD 1.04, 95% CI 0.33-1.76 kJ). Moses and standard HLL were not significantly different in terms of operation (MD -9.89, 95% CI -25.14 to 5.37 minutes) and fragmentation times (MD -1.71, 95% CI -11.81 to 8.38 minutes), as well as stone-free (odds ratio [OR] 1.04, 95% CI 0.73-1.49) and overall complication rates (OR 0.68, 95% CI 0.39-1.17). Conclusions: While perioperative outcomes were equivalent between Moses and standard HLL, Moses was associated with faster lasing time and stone ablation speeds at the expense of higher energy usage.

Organic Mixed-Valence Compounds and the Overhauser Effect in Insulating Solids.

Recent experiments have shown that the organic free radical 1,3-bisdiphenylene-2-phenylallyl (BDPA) can induce an Overhauser effect dynamic nuclear polarization in insulating solids, a feat previously considered not to be possible. Here, we establish that this peculiar ability of the BDPA radical stems from its mixed-valence nature and the ensuing intramolecular charge transfer. Using state-of-the-art DMRGSCF calculations, we confirm the class II mixed-valence nature of BDPA with the characteristic double-well potential energy surface, and we investigate the mechanism of the consequent electron hopping. A two-component vibronic Hamiltonian is then employed to compute the rate of electron hopping from a quantum dynamical time-propagation of the density matrix. The predicted hyperfine coupling oscillations indeed fall within the frequency range required for an Overhauser effect. The paradigm of mixed-valence compounds as a mining source opens many possibilities for the development and fine tuning of novel polarizing agents.

Biomarkers for hepatocellular cancer.

Hepatocellular carcinoma (HCC) is the third leading cause of cancer-related deaths worldwide. If diagnosed early, curative treatment options such as surgical resection, loco-regional therapies, and liver transplantation are available to patients, increasing their chances of survival and improving their quality of life. Unfortunately, most patients are diagnosed with late stage HCC where only palliative treatment is available. Therefore, biomarkers which could detect HCC early with a high degree of sensitivity and specificity, may play a crucial role in the diagnosis and management of the disease. This review will aim to provide an overview of the different biomarkers of HCC comprising those used in the diagnosis of HCC in at risk populations, as well as others with potential for prognosis, risk predisposition and prediction of response to therapeutic intervention.

Gender Differences in Impulse Control Disorders and Related Behaviors in Patients with Parkinson's Disease and its Impact on Quality of Life.

BACKGROUND: Dopaminergic medications administered to remedy motor symptoms in Parkinson's disease are associated with an enhanced risk for impulse control disorders (ICD) and related compulsive behaviors (ICD-RB). Thus, the present study focuses on investigating the gender difference in the prevalence of ICD-RBs in Indian PD patients on dopamine replacement therapy (DRT), its impact on quality of life and to identify ICDs relevant in Indian scenario apart from the criteria set in QUIP-RS. METHOD: This was a hospital-based observational cross-sectional study in which Parkinson's disease patients attending neurology clinic were included. Complete details of anti-parkinsonian therapy along with demographic and clinical variables were recorded on a predesigned Performa. Questionnaire for Impulsive-Compulsive Disorders in Parkinson's disease (QUIP), which is a validated quick screening tool, was used to detect ICD-RBs. The relative frequency and comparative impact of ICD on health-related quality of life (QOL) was studied using validated PDQ-39 Questionnaire. RESULTS: Out of 102 patients, at least one ICD or ICD-RB was present in 41.19% and ≥2 ICD-RBs were present in 15.59%. At least one ICD was present in 16.67%, any ICD-related compulsive behaviors was present in 34.31% patients. The most common was punding and compulsive medication use (12.75% each), followed by hobbyism (7.84%), compulsive eating (6.86%), pathological gambling (3.92%), and hypersexuality, walkabout, and compulsive shopping (2.94% each). ICDs not classified elsewhere such as trichotillomania were found 3 patients (2.94%). ICD-RBs showed a trend to be more frequent in women (44.82% women vs. 39.39% men). As compared with patients without ICD-RBs, those with ICD-RBs were found to have higher dose of LD and DA and higher Hoehn and Yahr stage. ICD-RBs have a negative impact on the quality of life of Parkinson's disease patients. CONCLUSION: ICDs and ICD-RBs have been included in the behavioral spectrum of nonmotor symptoms in PD. PD patients are at increased risk of developing ICD-RBs which interfere with important activities and have obligation in ordinary life, leading to legal and psychological consequences with a great impact on QOL.

The Effect of Focal Distance, Age, and Brightness on Near-Field Augmented Reality Depth Matching.

Many augmented reality (AR) applications operate within near-field reaching distances, and require matching the depth of a virtual object with a real object. The accuracy of this matching was measured in three experiments, which examined the effect of focal distance, age, and brightness, within distances of 33.3 to 50 cm, using a custom-built AR haploscope. Experiment I examined the effect of focal demand, at the levels of collimated (infinite focal distance), consistent with other depth cues, and at the midpoint of reaching distance. Observers were too young to exhibit age-related reductions in accommodative ability. The depth matches of collimated targets were increasingly overestimated with increasing distance, consistent targets were slightly underestimated, and midpoint targets were accurately estimated. Experiment II replicated Experiment I, with older observers. Results were similar to Experiment I. Experiment III replicated Experiment I with dimmer targets, using young observers. Results were again consistent with Experiment I, except that both consistent and midpoint targets were accurately estimated. In all cases, collimated results were explained by a model, where the collimation biases the eyes' vergence angle outwards by a constant amount. Focal demand and brightness affect near-field AR depth matching, while age-related reductions in accommodative ability have no effect.

Evaluation of positional accuracy of the Varian's exact-arm and retractable-arm support electronic portal imaging device using intensity-modulated radiotherapy graticule phantom.

PURPOSE: The aim of the present study was to compare the positional accuracy of varian's exact-arm (E-arm) and retractable-arm (R-arm) supporting electronic portal imaging device (EPID) systems (amorphous silicon flat-panel detector) using the intensity-modulated radiotherapy (IMRT) graticule phantom. MATERIALS AND METHODS: The known shifts of 0.5, 1.0, and 1.5 cm were introduced to the given phantom in longitudinal, lateral, and vertical directions, respectively, with respect to treatment couch of medical linear accelerator. The experiment was repeated for different gantry angle and varying source to imager distances (SIDs). The images were acquired for each shift at varying SIDs and beam orientations for both EPID supporting systems. The corresponding shifts obtained from treatment planning system (TPS) were recorded and compared. RESULTS: The known (expected) and observed (recorded from TPS) shifts obtained for different beam angles (namely, 0°, 90°, 180°, and 270° for anterior, left lateral, posterior, and right-lateral portal images, respectively) in the longitudinal, lateral, and vertical direction at varying SID were compared. The maximum shift in the observed value from the expected one was 3 and 2 mm, respectively, out of the all beam configuration for R-arm and E-arm. These shifts were randomly observed for all imager position and beam orientation. CONCLUSION: The IMRT graticule phantom is an effective tool to check the mechanical characteristic and consistency of different EPID supporting arms. The effect of EPID sag due to gravity (gantry and treatment couch) was not significant for detection of shift in patient's position. The E-arm support EPID has better mechanical stability and accuracy in detection of patient's position than that of R-arm.

Measurement of large angle Rayleigh scattering cross sections for 39.5, 40.1 and 45.4keV photons in elements with 26 ≤ Z ≤ 83.

The present work reports Rayleigh scattering cross section measurements for the 39.5keV (Sm- Kα2), 40.1keV (Sm-Kα1) and 45.4keV (Sm-Kß1,3) X-ray photons in 35 elements with 26 ≤ Z ≤ 83 at backward angle of 139°. The scattering measurements were performed in reflection mode geometrical set up involving a secondary photon source consisting of Samarium (62Sm) target excited by the 59.54keV γ-rays from the 241Am radioactive source. The scattered photons were detected using a low energy germanium (LEGe) detector. The product of detector efficiency, intensity of incident photons and other geometrical factors were determined by measuring the K X-ray yields from targets with 47 ≤ Z ≤ 59 and knowledge of the respective K X-ray fluorescence cross sections. The measured cross sections are compared with the theoretical cross sections based on the modified form factor (MF) formalisms and the second-order S-matrix approach. The experimental results demonstrate large deviations from the MF values for the elements with K shell binding energy (BK) in vicinity of the incident photon energy (Ein), which smooth out with inclusion of the anomalous scattering factors (ASFs). The S-matrix values, in general, agree with the measured cross sections for all the elements under investigation.

Matching and reaching depth judgments with real and augmented reality targets.

Many compelling augmented reality (AR) applications require users to correctly perceive the location of virtual objects, some with accuracies as tight as 1 mm. However, measuring the perceived depth of AR objects at these accuracies has not yet been demonstrated. In this paper, we address this challenge by employing two different depth judgment methods, perceptual matching and blind reaching, in a series of three experiments, where observers judged the depth of real and AR target objects presented at reaching distances. Our experiments found that observers can accurately match the distance of a real target, but when viewing an AR target through collimating optics, their matches systematically overestimate the distance by 0.5 to 4.0 cm. However, these results can be explained by a model where the collimation causes the eyes' vergence angle to rotate outward by a constant angular amount. These findings give error bounds for using collimating AR displays at reaching distances, and suggest that for these applications, AR displays need to provide an adjustable focus. Our experiments further found that observers initially reach ∼4 cm too short, but reaching accuracy improves with both consistent proprioception and corrective visual feedback, and eventually becomes nearly as accurate as matching.

Clinical and economic burden of emergency department visits due to gastrointestinal diseases in the United States.

OBJECTIVES: Gastrointestinal (GI) emergencies may cause substantial morbidity. Our aims were to characterize the national clinical and economic burden of GI visits to emergency departments (EDs) in the United States. METHODS: We performed an observational cross-sectional study using the 2007 Nationwide Emergency Department Sample, the largest US all-payer ED database, to identify the leading causes for ED visits due to GI diseases and their associated charges, stratified by age and sex. Logistic regression was used to analyze predictors of hospitalization after an ED visit. RESULTS: Of the 122 million ED visits in 2007, 15 million (12%) had a primary GI diagnosis. The leading primary GI diagnoses were abdominal pain (4.7 million visits), nausea and vomiting (1.6 million visits), and functional disorders of the digestive system (0.7 million visits). The leading diagnoses differed by age group. The fraction of ED visits resulting in hospitalization was 21.6% for primary GI diagnoses vs. 14.7% for non-GI visits. Women had more ED visits with a primary GI diagnosis than men (58.5 (95% CI 56.0-60.9) vs. 41.6 (95% CI 39.8-43.3) per 1000 persons), but lower rates of subsequent hospitalization (20.0% (95% CI 19.4-20.7%) vs. 24.0% (95% CI 23.3-24.6%)). There were no differences in hospitalization rates between sexes after adjustment by age, primary GI diagnosis, and Charlson Comorbidity Score. The total charges for ED visits with a primary GI diagnosis in 2007 were $27.9 billion. CONCLUSIONS: GI illnesses account for substantial clinical and economic burdens on US emergency medical services.