Facile Transfer Research Articles

P-369. Skilled Nursing Facility Characteristics Associated with Candida auris Transmission in Maryland

Abstract Background C. auris is a multi-drug resistant organism with high morbidity and mortality that is increasing throughout the United States. Skilled nursing facilities (SNFs) play a large role in transmission of this pathogen in healthcare settings. In this study, we compare characteristics of SNFs with and without C. auris transmission in Maryland. Comparison of Resident Characteristics Between Facilities with and without C. auris Transmission Methods We conducted a retrospective analysis of all 226 Maryland SNFs to identify characteristics associated with C. auris transmission from June 2019, when transmission was first detected in the state, to December 2022. C. auris transmission was defined as ≥ 2 cases that were epidemiologically linked to the same SNF. SNF resident and facility characteristics were obtained from the public database Long Term Care Focus (LTCFocus) and the Maryland Health Care Commission (MHCC). A Maryland-specific patient transfer network was built using data derived from Centers for Medicare and Medicaid Services (CMS) fee for service beneficiary claims data linked to the CMS Data Set (Figure 1). Centrality measures were calculated based upon patient transfer networks. We used bivariate analyses to compare facilities with and without C. auris transmission. Comparison of Centrality Measures (Connectedness)Between Facilities with and without C. auris Transmission. Results Fifteen SNFs had transmission of C. auris during the study period. SNFs with transmission had a greater number of residents (mean 141 v 95), higher resident acuity, higher percentage of black residents (64% v 34%) and higher percentage of residents on Medicaid (74% v 59%) (Table 1). The patient transfer network of SNFs with transmission generally had higher measures of centrality, including Betweenness Centrality and PageRank (Table 2). Based on the network analysis, facilities that influence and serves as a bridge between other facilities have a higher likelihood of transmission. Network Characterization of Patient Transfer Network in Maryland Using CMS Data. Conclusion Maryland SNFs with more central patient transfer networks and with a higher proportion of residents on Medicaid, Black residents, and acutely ill were more likely to have C. auris transmission. Additional analyses on interactions between facility characteristics and transfer networks are needed to help direct infection prevention efforts. Disclosures All Authors: No reported disclosures

Interfacility Transfer for VA-ECMO in Beta Blocker and Calcium Channel Blocker Overdoses: A Report of Two Cases

Introduction: Calcium channel blocker (CCB) and beta blocker (BB) overdoses are life-threatening conditions that can lead to vasoplegic and cardiogenic shock. Treatment involves a combination of vasopressors, calcium, glucagon, and/or high-dose insulin euglycemia therapy. The most severe overdoses may require venoarterial extracorporeal membrane oxygenation (VA-ECMO), which often results in interfacility transfers. This report describes two successful VA-ECMO transfers for refractory CCB/BB overdose. Case Reports: Case 1: A 56-year-old male developed severe hypotension after ingesting 40-45 tablets of 10 milligram (mg) amlodipine tablets. After initial treatment approaches were unsuccessful, an early interdisciplinary discussion facilitated timely cannulation at the initial facility and quick transfer for VA-ECMO initiation. The patient was discharged at his neurological baseline after 60 days. Case 2: A 19-year-old female presented to the emergency department after a polypharmacy ingestion including 60 tablets of 20 mg propranolol. An early interdisciplinary discussion between the medical intensive care unit, medical toxicology, and the ECMO team allowed for prompt transfer directly to the receiving hospital catheterization lab for VA-ECMO within three hours of the initial presentation. The patient was discharged to an inpatient psychiatric facility after nine days. Conclusion: Venoarterial extracorporeal membrane oxygenation for refractory shock due to CCB and BB overdoses can be a life-saving intervention. Interfacility transfer of poisoned patients for VA-ECMO is logistically challenging, which can delay the appropriate care for patients with an otherwise morbid prognosis. A streamlined interfacility transfer protocol with multidisciplinary collaboration can help optimize outcomes.

Synthesis, Antioxidant, and Antidiabetic Potential of Ferrocenylmethylnucleobase Compounds: In Vitro, In Silico Molecular Docking, DFT Calculation, and Molecular Dynamic Simulations

ABSTRACTThis study presents the synthesis and characterization of a novel series of ferrocenylmethylnucleobase compounds, namely, FcMeAd, FcMeCy, FcMeTh, and (FcMe)₂Ad with promising antioxidant and antidiabetic properties. Spectroscopic techniques confirmed their sandwich‐like geometry, with the nucleobase moiety coordinated to the ferrocene unit. Density functional theory (DFT) optimization revealed alignment with existing crystallographic data and indicated low frontier molecular orbital (FMO) energy gaps, suggesting facile intramolecular charge transfer and potential biological activity. The antidiabetic activity was evaluated in vitro through inhibition assays targeting α‐glucosidase and α‐amylase enzymes, which was supported by in silico molecular docking studies. Among the compounds, FcMeTh exhibited the highest antidiabetic and antioxidant properties due to the presence of carbonyl and amide functionalities, along with an electron‐donating methyl group. Molecular dynamics (MD) simulations confirmed high binding affinity and structural stability of the docked compounds, with strong interactions with the target enzymes, further validating the potential of these compounds as effective inhibitors. Pharmacokinetic and ADMET evaluations indicated their nontoxic, noncarcinogenic nature and suitability for oral administration. The combined in vitro and in silico findings, including the critical insights from MD simulations, suggest that these ferrocenylmethylnucleobase compounds, especially FcMeTh, possess enhanced antioxidant and antidiabetic properties. This highlights their potential as promising therapeutic agents for managing oxidative stress and Type 2 diabetes.

P2-Na0.67Mn0.7Ni0.2Co0.1O2 stabilized by optimal active facets for sodium-ion batteries.

Considering factors such as crustal reserves, atomic mass, redox potential and energy density, sodium-ion batteries (SIBs) are regarded as the most promising alternative to lithium-ion batteries (LIBs). Transition metal-based layered oxides, especially typical NaxMnO2, stand out among cathode materials due to their low cost and high energy density. However, NaxMnO2 cathodes face several challenges, including Jahn-Teller distortion, manganese dissolution, structural collapse, irreversible phase transition and significant capacity loss. In addition, the significant changes in lattice parameters can lead to the formation of cracks and nanovoids. It has been reported that optimizing the assembly of surface facets can be beneficial to electrochemical properties. In this work, Na0.67MnO2 (NMO) with a multilayered structure featuring (distinct {010} active facets and Na0.67Mn0.7Ni0.2Co0.1O2 (NMNCO) with a homogeneous polyhedra structure featuring distinct {001} active facets were synthesized. The initial charge capacity of NMNCO reached 110.1mA h g-1 at a current density of 10mA g-1. After 100 cycles at 100mA g-1, it displayed a good cycling retention rate of 82.1%. The distribution of relaxation times (DRT) reveals the facile transfer of Na+ ions in the NMNCO cathode. In addition, the effects of Ni and Co are revealed, and the mechanism underlying the relationship between distinct surface facet and crack formation is studied.

Utilization of free referral transport services- 102 or Mahatari Express under Janani Shishu Suraksha Karyakram in rural block of Raipur, Chhattisgarh

Background: Mahatari Express or 102 [an initiative of Family and Health welfare department (Government of India) and Government of Chhattisgarh under Janani Shishu Suraksha Karyakram (JSSK project)] is the dedicated vehicle for cashless transport of pregnant women from home to hospital (pick up), hospital to home (drop back) and hospital to hospital (inter facility transfer) for institutional delivery. Objective was to assess the utilization of free referral transport (Mahatari express) service in rural block of Chhattisgarh. Methods: A community based cross-sectional study done in selected 32 villages of Dharsiwa, a rural block of Raipur district among 352 mothers having child less than one year using multistage random sampling from July 2015 to June 2016. Results: Among all mothers, 72% mothers delivered in the public health facility. Out of this mother who delivered in government facility, 161.27% availed this Mahatari express to reach the facility for delivery while 66.80% availed only drop back facility from home to institute. 57.70% mothers benefited with both the way cost free transport using Mahatari Express. Conclusions: Though Mahatari express was started in the year 2013 in Chhattisgarh, but less percentage of pregnant females had utilized both way free referral services to government facility during delivery.

(Invited) Low-Temperature Processing of Mixed Conducting Oxides: Control of Defects, Transport, and Reactions Away from Equilibrium

Low-to-intermediate temperature processing and use of mixed conducting oxides targets the following potential benefits: ultra-fine nanostructuring with avoidance of coarsening, control of surface chemistry, lower energy consumption, integration with thermally sensitive components, and slower degradation vs. conventional high temperature synthesis and use. In this lower temperature regime, we have pursued two routes for non-equilibrium control of defect chemistry and therefore properties of mixed ionic/electronic conductors (MIECs) in the ferrite perovskite family: crystallization and illumination.Room-temperature growth followed by mild anneals to induce crystallization has proven to yield superior oxygen surface exchange kinetics, attributed to development of facile charge transfer and pristine surface chemistry in our prior work. The close link between crystallinity and oxygen stoichiometry appears to play an important role in the structural evolution and electrical response. However the effect of evolving crystallinity on the ionic conductivity has not been studied in-depth. Therefore we recently pursued an approach combining in-situ synchrotron grazing-incidence X-ray diffraction with ac and dc electrical methods on thin-film blocking electrode cells to evaluate evolution of transference numbers during crystallization. In certain ferrite films we observe a ~2 orders-of-magnitude increase in ionic conductivity during crystallization, while the electronic conductivity increases much more. Through the process, we demonstrate that it is possible to turn a predominantly ionic conductor into a predominantly electronic conductor - and to access almost any ionic transference number in between - simply by controlling the degree of crystallinity. [1]Oxygen stoichiometry can alternatively be controlled at low-to-intermediate temperatures through application of low fluence above-gap illumination. We have shown in certain non-dilute ferrite films that UV light causes oxygen to enter the films from the gas phase with kinetics limited by the oxygen surface-exchange reaction, which is largely unchanged by the presence of excited carriers. We explain the response through simulations of excited state defect equilibria and transient absorption spectroscopy measurements. [2]Together these processing strategies indicate that low-temperature control of oxygen stoichiometry is feasible in mixed conductors, enabling wide tailoring of properties and potential for use in low-to-intermediate temperature solid-state ionic devices.[1] H.B. Buckner, J. Simpson-Gomez, A. Bonkowski, K. Rubartsch, H. Zhou, R.A. De Souza, N.H. Perry (in review)[2] E. Skiba, H.B. Buckner, G. McKnight, C. Lee, R. Wallick, R. van der Veen, E. Ertekin, N.H. Perry (in review)We gratefully acknowledge funding from the US Department of Energy, Basic Energy Sciences, under DOE Early Career grant DE-SC-0018963 and from the US National Science Foundation, through the University of Illinois at Urbana-Champaign Materials Research Science and Engineering Center DMR-2309037.

Lawn-inspired porous protection layers consisting of super-lithiophilic Ag arrays for high-performance Li metal anodes

A lawn-inspired porous and super-lithiophilic protection layer which consists of leaf-like Ag arrays has been successfully constructed on the metallic Li foil surface through a facile and scalable transfer printing method assisted by the mechanical rolling process. Benefited from the superior merits of these lawn-inspired Ag protection layers (L-Ag), Li dendrite growth and structure collapse have been effectively prohibited by the L-Ag@Li composite anodes. Therefore, the L-Ag@Li anodes exhibit outstanding cycling stability with extremely low overpotential (10 mV at 1 mA cm−2 after 500 cycles (1000h)) in symmetric cells and high discharge capacity (147 mAh g−1 at 1C after 200 cycles) in coin-type NCM811||L-Ag@Li full cells. The encouraging results suggest the enormous potential of Li metal anodes protected by lawn-inspired porous Ag array layers for energy-storage applications.

Photothermal and colorimetric detection of cholesterol using hollow ruthenium nanoparticles

Nanozyme, an artificial enzyme with some advantages that compensate for the inherent shortcomings of natural enzymes have been explored. Among the various nanoparticles, those with a hollow structure have the advantage of enabling facile transfer of reactants and exhibiting a high surface-to-volume ratio. Herein, we synthesized hollow ruthenium nanoparticles (HRNs) by the galvanic replacement reaction. Transmission electron microscopy confirmed an average size of 32 nm and a shell thickness of about 2.5 nm. HRNs showed superior catalytic activity compared to natural enzymes due to the advantages of their hollow structure. Based on enhanced catalytic activity, HRNs were applied to cholesterol detection using 2,2′-azino-bis (3-ethylbenzo-thiazoline-6-sulfonic acid) (ABTS) and 3,3′,5,5′-tetramethylbenzidine (TMB). These common chromogenic substrates in colorimetric methods have strong absorbance in the UV–visible and near-infrared (NIR) regions in their oxidized forms. Therefore, both substrates can serve as probes in photothermal and colorimetric assays. Two oxidized substrates absorbed the NIR laser (808 nm) and released energy in the form of heat. Consequently, the temperature of the reaction solution increased in proportion to the cholesterol concentration. In the cholesterol detection assay using ABTS, linear ranges were ranged from 0.08 to 10 mM (R2 = 0.998) for the colorimetric assay and from 0.08 to 2.5 mM (R2 = 0.996) for the photothermal assay, respectively. The limits of detection were determined to be 12.3 μM in the colorimetric method and 43.5 μM in the photothermal method. These results demonstrate that HRN is an excellent substitute for natural enzymes and a promising material for analytical applications.

Crystal structure, structural geometry, and molecular motion of organic–inorganic perovskite [N(CH3)4]2MnCl4 crystals at phases I, II, and III

Various aspects of the new development of organic-inorganic hybrid [N(CH3)4]2MnCl4 single crystals have been discussed. The phase transition temperatures were determined to be 268 K (TC2) and 291 K (TC1), and the thermodynamic stability was maintained at temperatures up to 669 K. The crystal structures at 250 K (phase III), 275 K (phase II), and 300 K (phase I) are monoclinic, orthorhombic, and orthorhombic, respectively. Notably, while the 1H and 13C chemical shifts gradually changed near TC1 and TC2, the 14N resonance frequency exhibited a split in the number of signals near TC1. Furthermore, the shorter spin-lattice relaxation time T1ρ of 1H than that of 13C suggests facile energy transfer for1H. Additionally, analysing the temperature dependencies of T1ρ for 13C revealed that the activation energy Ea in phase I is approximately five times greater than those in phases III and II. The high Ea observed in phase I primarily stems from the collective motion of the N(CH3)4 group, which contrasts with the considerable freedom observed for the CH3 group in phases III and II. These distinctive physical properties suggest potential applications for [N(CH3)4]2MnCl4 as an organic‒inorganic hybrid material.

Patient-Level Factors, Outcomes, and Costs Associated With Facility Transfer Following Total Knee Arthroplasty: A Retrospective Database Study

BackgroundPatient disposition following total knee arthroplasty (TKA) has major implications for patient outcomes and costs. Current studies are limited in sample size and dates of data collection. We evaluated patient factors, outcomes, and costs associated with disposition to a facility following TKA. MethodsThis was a retrospective cohort study including 1,906,670 patients undergoing TKA from a nationwide database, from the years 2016 to 2020. Of these, 25,485 (1.34%) patients were transferred to a facility for rehabilitation. Demographic data, hospital-related outcomes, and postoperative complications were collected. Multivariate regression was performed to assess outcomes associated with facility transfer for rehabilitation. ResultsPatients were more likely to be transferred if they were women (odds ratio (OR) = 1.10; P < 0.001), greater than 80 years (OR = 2.25; P < 0.001), had an increased Elixhauser comorbidity index (OR = 1.38; P < 0.001), or were in the lowest income quartile (OR = 1.38; P < 0.001). Transferred patients were more likely to experience medical (OR = 1.92; P < 0.001) and surgical complications (OR = 2.74; P < 0.001), including vascular complications (OR = 2.07; P < 0.001), neurologic complications (OR = 5.72; P < 0.001), and dislocation (OR = 2.01; P < 0.001). They also had greater hospital lengths of stay (OR = 5.27; P < 0.001) and hospital charges (OR = 1.88; P < 0.001); however, they were less likely to undergo reoperation within 30 days (OR = 0.61; P = 0.002). ConclusionsElderly, lower income patients who had more comorbidities are more likely to be transferred to a facility following TKA. While there are associated increased costs, complications, and hospital lengths of stay, there are lower rates of reoperation for those who transferred to a facility after TKA.

Laser exfoliated 2D MXene for supercapacitor applications

MXenes-based compounds, particularly Ti3C2Tx, have been studied intensively as electrodes for supercapacitors due to their layered structure and high conductivity, enabling facile ion diffusion and charge transfer. However, tight restacking of the 2D layers in these materials limits their practical, accessible surface area, thereby impeding their capacity and rate capability performance. To mitigate this phenomenon, we present a new approach using a processing method based on laser beam irradiation to modify Ti3C2Tx films. We found that the laser treatment induces chemical and morphological changes, ultimately optimizing the stacking arrangement of the MXene electrodes and consequently enhancing their capacity in both neutral and acidic electrolytes. Furthermore, the laser-modified MXene electrodes demonstrate excellent rate capabilities, showing 84 % retention at extreme rates of 0.5 V compared to only 33 % of the original Ti3C2Tx electrodes. Finally, we discuss the chemical and physical changes induced by the laser treatments and their influence on the electrochemical behavior of the lasered MXene. The principles of laser exfoliation discovered in this study can be implemented in broader 2D materials for various applications.

Revealing the Role of Electronic Effect to Modulate the Photophysics and Z-Scan Responses of o-Locked GFP Chromophores.

Three novel core green fluorescent protein (GFP) chromophore analogues, based on a doubly locked conformation and variable electronic effects by replacing one hydrogen with bromine, iodine, and methyl, respectively, have been synthesized to modulate the push-pull effect. These chromophores exhibited intramolecular H-bonding, as evidenced by single-crystal X-ray and 1H NMR studies. The fluorescence quantum yields (ϕf) of all of the chromophores were found to be more than an order of magnitude higher (∼0.2) than the unlocked chromophores (∼0.01). It was found that the electronic effect did affect the nonradiative rates, as the quantum yields were found to vary with respect to different analogues in the same solvents. The effect of the push-pull effect was also evident by a higher Stokes-shifted emission in the case of the methyl derivative with respect to the bromo- and iodo-analogues. Furthermore, the emission spectra of these GFP chromophores were found to show positive solvatochromism, which was supported by a quantum chemical calculation. A detailed study, correlating the observed spectral changes with various solvent functions and supported by computational results, established a facile proton transfer, followed by twisted intramolecular charge transfer (TICT) to be the major nonradiative channels of these chromophores. Besides, a completely novel usage of these chromophores was explored for the first time by studying their third-order nonlinear optical characteristics in DMSO using a single-beam Z-scan technique. All of the chromophores exhibited tunable nonlinear refraction (NLR) and nonlinear absorption (NLA) properties that depend upon different substituent groups present in the chromophores. Here, the NLR was due to the effect of self-defocusing, whereas the NLA was triggered by reverse saturable absorption, which is attributed to the two-photon absorption (TPA) process. Surprisingly, the efficiency of the TPA ability of the chromophores was found to be a function of the induced electronic effect. Hence, this work opens a new route for the utility of the ortho-locked GFP chromophores in the field of nonlinear optical applications.

Extending the π‐Conjugation of a Donor‐Acceptor Covalent Organic Framework for High‐Rate and High‐Capacity Lithium‐Ion Batteries

AbstractRealizing high‐rate and high‐capacity features of Lihium‐organic batteries is essential for their practical use but remains a big challenge, which is due to the instrinsic poor conductivity, limited redox kinetics and low utility of organic electrode mateials. This work presents a well‐designed donor‐acceptor Covalent Organic Framework (COFs) with extended conjugation, mesoscale porosity, and dual redox‐active centers to promote fast charge transfer and multi‐electron processes. As anticipated, the prepared cathode with benzo [1,2‐b:3,4‐b′:5,6‐b′′] trithiophene (BTT) as p‐type and pyrene‐4,5,9,10‐tetraone (PTO) as n‐type material (BTT‐PTO‐COF) delivers impressive specific capacity (218 mAh g−1 at 0.2 A g−1 in ether‐based electrolyte and 275 mAh g−1 at 0.2 A g−1 in carbonate‐based electrolyte) and outstanding rate capability (79 mAh g−1 at 50 A g−1 in ether‐based electrolyte and 124 mAh g−1 at 10 A g−1 in carbonate‐based electrolyte). In addition, the potential of BTT‐PTO‐COF electrode for prototype batteries has been demonstrated by full cells of dual‐ion (FDIBs), which attain comparable electrochemical performances to the half cells. Moreover, mechanism studies combining ex situ characterization and theoratical calculations reveal the efficient dual‐ion storage process and facile charge transfer of BTT‐PTO‐COF. This work not only expands the diversity of redox‐active COFs but also provide concept of structure design for high‐rate and high‐capacity organic electrodes.

Extending the π-Conjugation of a Donor-Acceptor Covalent Organic Framework for High-Rate and High-Capacity Lithium-Ion Batteries.

Realizing high-rate and high-capacity features of Lihium-organic batteries is essential for their practical use but remains a big challenge, which is due to the instrinsic poor conductivity, limited redox kinetics and low utility of organic electrode mateials. This work presents a well-designed donor-acceptor Covalent Organic Framework (COFs) with extended conjugation, mesoscale porosity, and dual redox-active centers to promote fast charge transfer and multi-electron processes. As anticipated, the prepared cathode with benzo [1,2-b:3,4-b':5,6-b''] trithiophene (BTT) as p-type and pyrene-4,5,9,10-tetraone (PTO) as n-type material (BTT-PTO-COF) delivers impressive specific capacity (218 mAh g-1 at 0.2 A g-1 in ether-based electrolyte and 275 mAh g-1 at 0.2 A g-1 in carbonate-based electrolyte) and outstanding rate capability (79 mAh g-1 at 50 A g-1 in ether-based electrolyte and 124 mAh g-1 at 10 A g-1 in carbonate-based electrolyte). In addition, the potential of BTT-PTO-COF electrode for prototype batteries has been demonstrated by full cells of dual-ion (FDIBs), which attain comparable electrochemical performances to the half cells. Moreover, mechanism studies combining ex situ characterization and theoratical calculations reveal the efficient dual-ion storage process and facile charge transfer of BTT-PTO-COF. This work not only expands the diversity of redox-active COFs but also provide concept of structure design for high-rate and high-capacity organic electrodes.

Charge separation by switching heterojunction system from Type-II to S-scheme for enhanced photocatalytic activity: Environmental detoxification and H2 production

The development of highly efficient photocatalysts is essential for harnessing solar energy for pollutant degradation and hydrogen (H2) production. This study provides a novel ternary S-scheme photocatalyst (Fe2O3/Bi2O3/g-C3N4), prepared from optimized binary 20-Bi-C via a simple electrostatic self-assembly method for the first time. Using various methods including UV–vis DRS, PL, ESR, photocurrent, Mott-Schottky, XPS, XRD, FTIR, SEM, TEM, and BET, the optical, structural, and morphological characteristics of the produced materials were fully studied. The photocatalytic performance of as-manufactured materials was evaluated through the degradation of the Ciprofloxacin (CIP) and H2 production. Under optimized conditions determined by the RSM method, a maximum CIP degradation of 97.20 % was achieved at a rate of 0.053 min−1, with the catalyst dosage: 0.44 g/l, CIP concentration: 26.07 mg/l, pH: 6.29 and Time: 63.01. The optimized heterojunction exhibited an exceptional photocatalytic H2 generation rate of 2428 μmol·g−1·h−1 within 2 h, surpassing the binary 20-Bi-C photocatalyst by 1.3 times. Furthermore, after five continuous cycles, the 5-Fe2O3/Bi-C photocatalyst showed good chemical stability and reusability, sustaining a degradation rate of over 96 % and a TOC removal of 80 %. Experiments on the identification of free radicals have demonstrated the important roles that O2−, h+, and OH species play in the photocatalytic process. The enhancement mechanism of 5-Fe2O3/Bi-C involves the successful synthesis of Fe2O3/Bi-C photocatalyst with well-aligned positions of band gap edges, enabling the facile charge transfer through S-Scheme mechanism. Furthermore, the study investigates the impact of environmental factors, including solution pH, water matrices, and the efficiency of the synthesized photocatalyst on other organic pollutants. The photocatalytic degradation behavior of CIP is predicted using LC-MS analysis. This work provides a new method for building S-scheme heterojunctions by creatively converting the type-II heterojunction system to an S-scheme by metal oxide doping.

Uncovering a general oxidation model of nitrogen-containing oxidant in N-heterocyclic carbene (NHC) catalyzed oxidative reactions of aldehydes

Predicting how oxidants interact with reactive partners to alter the oxidation mechanism is a significant challenge in carbene catalysis. In this study, we investigated several examples to address this issue. Using density functional theory (DFT), we explored N-heterocyclic carbene (NHC)-catalyzed oxidative [2 + 4] annulations of aliphatic aldehydes with α,β-unsaturated ketones, focusing on the role of nitrogen-containing oxidant. Our computational results reveal that a hydrogen-bonding bridge framework, formed during oxidation, is crucial for facilitating π···π stacking interactions between the oxidant and the NHC catalyst. These interactions significantly lower the oxidation energy barrier, enabling a facile hydride transfer. This mechanism was validated across other reactions involving different nitrogen-containing oxidants. Frontier molecular orbital (FMO) analysis demonstrates how the NHC catalyst lowers the cycloaddition energy barrier by altering the orbital overlap from shoulder-to-head to head-to-head. Additionally, this elucidates the origin of stereoselectivity by highlighting energy differences between two reacting components at cycloaddition transition states. The nucleophilic index further predicts the preferred ketone attack site. This work advances our understanding of oxidation mechanisms involving nitrogen-containing oxidants and offers valuable insights for designing potent organic oxidants in organocatalytic oxidative reactions.

Theoretical Investigation of the Effects of Aldehyde Substitution with Pyran Groups in D-π-A Dye on Performance of DSSCs.

This work investigated the substitution of the aldehyde with a pyran functional group in D-π-aldehyde dye to improve cell performance. This strategy was suggested by recent work that synthesized D-π-aldehyde dye, which achieved a maximum absorption wavelength that was only slightly off the threshold for an ideal sensitizer. Therefore, DFT and TD-DFT were used to investigate the effect of different pyran substituents to replace the aldehyde group. The pyran groups reduced the dye energy gap better than other known anchoring groups. The proposed dyes showed facile intermolecular charge transfer through the localization of HOMO and LUMO orbitals on the donor and acceptor parts, which promoted orbital overlap with the TiO2 surface. The studied dyes have HOMO and LOMO energy levels that could regenerate electrons from redox potential electrodes and inject electrons into the TiO2 conduction band. The lone pairs of oxygen atoms in pyran components act as nucleophile centers, facilitating adsorption on the TiO2 surface through their electrophile atoms. Pyrans increased the efficacy of dye sensitizers by extending their absorbance range and causing the maximum peak to redshift deeper into the visible region. The effects of the pyran groups on photovoltaic properties such as light harvesting efficiency (LHE), free energy change of electron injection, and dye regeneration were investigated and discussed. The adsorption behaviors of the proposed dyes on the TiO2 (1 1 0) surface were investigated by means of Monte Carlo simulations. The calculated adsorption energies indicates that pyran fragments, compared to the aldehyde in the main dye, had a greater ability to induce the adsorption onto the TiO2 substrate.

Financial toxicity and acute injury in the Kilimanjaro region: An application of the Three Delays Model.

Trauma and injury present a significant global burden-one that is exacerbated in low- and middle-income settings like Tanzania. Our study aimed to describe the landscape of acute injury care and financial toxicity in the Kilimanjaro region by leveraging the Three Delays Model. This cross-sectional study used an ongoing injury registry and financial questionnaires collected at Kilimanjaro Christian Medical Centre (KCMC) in Moshi, Tanzania from December 2022 until March 2023. Financial toxicity measures included catastrophic expenditure and impoverishment, in accordance with World Health Organization standards. Descriptive analysis was also performed. Most acute injury patients that presented to the KCMC Emergency Department experienced financial toxicity due to their out-of-pocket (OOP) hospital expenses (catastrophic health expenditure, CHE: 62.8%; impoverishment, IMP: 85.9%). Households within our same which experienced financial toxicity had more dependents (CHE: 18.4%; IMP: 17.9% with ≥6 dependents) and lower median monthly adult-equivalent incomes (CHE: 2.53 times smaller than non-CHE; IMP: 4.27 times smaller than non-IMP). Individuals experiencing financial toxicity also underwent more facility transfers with a higher surgical burden. Delay 1 (decision to seek care) and Delay 2 (reaching appropriate care facility) could be significant factors for those who will experience financial toxicity. In the Tanzanian healthcare system where national health insurance is present, systematic expansions are indicated to target those who are at higher risk for financial toxicity including those who live in rural areas, experience unemployment, and have many dependents.

Factors associated with transfer from assisted living facilities to a nursing home: National Health Aging Trends Study 2011-2019.

Residents of assisted living facilities (ALF) transfer to a nursing home when they require a higher level of care, but limited research has examined risk factors for transfer to a nursing home. The aims of this study were to identify (1) baseline factors associated with transfer to a nursing home and (2) time-varying factors associated with transfer to a nursing home over 8 years, using a national dataset from the National Health Aging Trends Study (NHATS). NHATS participants were included in this study if they: (1) resided in ALF from Round 1 (2011) through Round 8 (2018); (2) completed the sample person (SP) interview at baseline; (3) were admitted to ALF at age 65 years or older. We conducted Cox proportional hazards regression to examine candidate predictors (difficulty with basic activities of daily living (ADL), chronic conditions, hospitalization, sleep disturbances, mental health, physical performance, self-reported health, participation in social and physical activity, and sociodemographic) associated with transfer to a nursing home. Employing backward elimination, we built parsimonious final models for analysis. The analytic sample included 970 participants of whom 143 transferred to nursing homes over 8 years. Those who had a better physical performance at baseline (HR = 0.83, 95% CI = 0.79-0.88) and were college educated (HR = 0.58, 95% CI = 0.36-0.92) demonstrated a significantly lower risk for transfer to a nursing home over 8 years. Residents who maintained physical activity (HR = 0.56, 95% CI = 0.37-0.86), better physical performance (HR = 0.87, 95% CI = 0.80-0.94), and difficulty with fewer basic ADLs (HR = 1.13, 95% CI = 1.02-1.26) were at lower risk for transfer to a nursing home over 8 years. Our findings can be used to identify older adults in ALFs at risk of transfer to a nursing home. Strategies to promote physical function and physical activity could avoid/delay the need to transfer. Helping older residents to age in place will have important health and economic benefits.

Ru-Mn pair-site triggers key oxygen intermediate for enhanced acidic oxygen evolution reaction kinetics

Charge and spin regulation of electrons are identified as a vital factor in improving the oxygen evolution reaction (OER) catalytic activity. Nevertheless, the influence of surface reconstruction on charge and spin structure under complex catalytic reaction conditions has been unintentionally neglected. Correct understanding and targeted regulation of surface reconstruction are the key to prepare high active catalysts. Herein, variable valence states Mn is adopted to regulate Ru-NC, which serves as a model to reduce the localization of Ru 4d structure and stimulate facile charge transfer, achieving accelerated surface reconstruction to generate Ru-O active ingredient with high active to acidic water oxidation. Doping Mn not only accelerates surface reconstruction, but also improves durability by eliminating Ru peroxidation due to Mn-buffered charge compensation. The enhancement of OER activity results from the Mn and O induced Ru spin states to change from intermediate spin to low spin, thereby weakening the interaction with *O intermediates, and promoting *OH adsorption, which benefits the initial step of OER. This study not only provides a strategy to achieve directional reconstruction with the help of metal site asymmetry, but also provides a thorough comprehension of charge and spin dependent acidic OER kinetics.