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This study introduces a facile method for the substrate-independent deposition of pheomelanin-like films, revealing unique and promising electrical characteristics. The conventional darkening of a dopamine solution at a basic pH was significantly delayed by the addition of l-cysteine, resulting in a distinctive temporal pattern: an initial quiescent period without apparent color change followed by an abrupt and explosive burst. Surprisingly, within the quiescent period, the deposition of ultrathin and smooth pheomelanin-like films was observed, in addition to rough and thick films formed after the burst. Regardless of thickness or texture, these films exhibited common chemical properties, including moisture-capturing capability and dark- and bright-state conductivities. Particularly noteworthy were consistent photocurrent responses under bias voltage across various pheomelanin-like films, which were not observed in polydopamine films, highlighting the influential role of l-cysteine addition. These findings present a novel avenue for the potential application of pheomelanin-like films in bioelectronics, emphasizing their distinct electrical characteristics and prompting further exploration into their intricate conductive mechanisms. The study contributes to advancing our understanding of melanin-based materials and their potential in diverse scientific and technological domains.
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Oxygen evolution reaction (OER) plays a crucial role as a counter half-reaction for both electrochemical hydrogen production through water splitting and the generation of valuable carbon compounds via CO2 reduction. To overcome the sluggish kinetics of the OER, significant efforts have been devoted to developing cost-effective, sustainable, and efficient electrocatalysts, with transition-metal-based catalysts emerging as promising candidates. Herein, we successfully synthesized a core-shell type nanostructure of Fe-doped CoMoOx/CoMoOx (CMFO), which exhibits excellent electrocatalytic properties for OER. The presence of an amorphous layer of Fe-doped CoMoOx with abundant oxygen vacancies, along with the stability of a key OER intermediate, *O, contributes to the enhanced activity of CMFO catalyst compared to pristine CoMoOx (CMO). The optimized catalyst of CMFO-550 achieved much lower overpotential and Tafel slope and also exhibited better remarkable long-term stability for over 90 h compared to CMO-550. These findings highlight the potential of CMFO-550 as a cost-effective and highly efficient electrocatalyst for the OER. The successful development of this core-shell nanostructure opens up a new opportunity for the design and synthesis of advanced electrocatalysts for the OER, with implications for various applications in energy conversion and storage.
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A novel class of o-carboranyl luminophores, 2CB-BuDABNA (1) and 3CB-BuDABNA (2) is reported, in which o-carborane moieties are incorporated at the periphery of the B,N-doped multi-resonance thermally activated delayed fluorescence (MR-TADF) core. Both compounds maintain the inherent local emission characteristics of their MR-emitting core, exhibiting intense MR-TADF with high photoluminescence quantum yields in toluene and rigid states. In contrast, the presence of the dark lowest-energy charge transfer state, induced by cage rotation in THF, is suggested to be responsible for emission quenching in a polar solvent. Despite the different arrangement of the cage on the DABNA core, both 1 and 2 show red-shifted emissions compared to the parent compound BuDABNA (3). By utilizing 1 as the emitter, high-efficiency blue organic light-emitting diodes (OLEDs) are achieved with a remarkable maximum external quantum efficiency of 25%, representing the highest reported efficiency for OLEDs employing an o-carboranyl luminophore as the emitter.
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One-dimensional ZnO nanorods (NRs) have been extensively studied as photoanodes because of their unique optical properties, high electron mobility, and suitable band positions for water oxidation. However, their practical efficiency is often compromised by chemical instability during water oxidation and high carrier recombination rates. To overcome this issue, precise morphological control of ZnO@ZnWO4 core-shell structured photoanodes, featuring a ZnO core and a ZnWO4 shell was used. This was accomplished by depositing WO3 onto hydrothermally grown ZnO NRs using the thermal chemical vapor deposition process. The photoelectrochemical performance of ZnO@ZnWO4 with an optimized morphology outperforms that of pristine ZnO NRs. Systematic optical and electrochemical analyses of ZnO@ZnWO4 demonstrated that the enhancement is attributed to the enhanced charge transfer efficiency facilitated by the optimized ZnWO4 shells.
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Most women in homeless populations are mothers, the majority being single mothers. Retaining child custody is challenging in homeless circumstances. Prospective longitudinal studies are needed to follow the moving pieces of housing and child custody in the context carefully-assessed psychiatric and substance use disorders over time. A 2-year prospective longitudinal study of an epidemiologic sample of individuals with literal homelessness included 59 mothers. Annual assessments included structured diagnostic interviews, detailed assessment of homeless circumstances, urine drug testing, and service use documented by both self report and data from agencies serving these individuals. More than one-third of the mothers consistently lacked child custody throughout the course of the study and the proportions of mothers with child custody did not increase significantly. Nearly one-half of the mothers had a current year drug use disorder at baseline, including cocaine disorder in most. Continuing lack of child custody over time was associated with longitudinal lack of housing and use of drugs. The importance of drug use disorders in the longitudinal course of child custody points to a critical need for formal substance abuse treatment, not just initiatives to decrease drug use, in helping mothers regain and maintain custody of their children.
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Designing multi-resonance (MR) emitters that can simultaneously achieve narrowband emission and suppressed intermolecular interactions is challenging for realizing high color purity and stable blue organic light-emitting diodes (OLEDs). Herein, a sterically shielded yet extremely rigid emitter based on a triptycene-fused B,N core (Tp-DABNA) is proposed to address the issue. Tp-DABNA exhibits intense deep blue emissions with a narrow full width at half maximum (FWHM) and a high horizontal transition dipole ratio, superior to the well-known bulky emitter, t-DABNA. The rigid MR skeleton of Tp-DABNA suppresses structural relaxation in the excited state, with reduced contributions from the medium- and high-frequency vibrational modes to spectral broadening. The hyperfluorescence (HF) film composed of a sensitizer and Tp-DABNA shows reduced Dexter energy transfer compared to those of t-DABNA and DABNA-1. Notably, deep blue TADF-OLEDs with the Tp-DABNA emitter display higher external quantum efficiencies (EQEmax =24.8 %) and narrower FWHMs (≤26â nm) than t-DABNA-based OLEDs (EQEmax =19.8 %). The HF-OLEDs based on the Tp-DABNA emitter further demonstrate improved performance with an EQEmax of 28.7 % and mitigated efficiency roll-offs.
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Three donor-acceptor-type thermally activated delayed fluorescence (TADF) emitters (PXZBAO (1), PXZBTO (2), and PXZBPO (3)) comprising a phenoxazine (PXZ) donor and differently π-expanded boron-carbonyl (BCO) hybrid acceptor units are proposed. The emitters exhibit red (1) to orange (3) emissions with an increase in the π-expansion in the BCO acceptors. The control of the strength of local aromaticity for the BCO unit and the corresponding LUMO level is attributed to inducing the unusual emission color shifts. The photoluminescence quantum yield and delayed fluorescence lifetime of the emitters are also adjusted by the π-expansion. Notably, although 1 possesses a 3nπ* state in the acceptor unit as a local triplet excited state (3LE, T2), the T2 states of 2 and 3 mainly comprise a 3ππ* state in the acceptor. Consequently, all of the emitters exhibit strong spin-orbit coupling between their T2 and excited singlet (S1) states, leading to a fast reverse intersystem crossing with rate constants of â¼106 s-1. By employing the emitters as dopants, we realize efficient red-to-orange TADF-OLEDs. Maximum external quantum efficiencies of 17.7% for the yellowish-orange (3), 15.5% for the orange (2), and 13.9% for the red (1) devices are achieved, and the values are very close to the theoretical limit predicted from the optical simulation.
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OBJECTIVE: Stroke caused from large vessel occlusion (LVO) has emerged as the most common stroke subtype worldwide. Intravenous tissue plasminogen activator administration (IV-tPA) and additional intraarterial thrombectomy (IA-Tx) is regarded as standard treatment. In this study, the authors try to find the early recanalization rate of IV-tPA in LVO stroke patients. METHODS: Total 300 patients undertook IA-Tx with confirmed anterior circulation LVO, were analyzed retrospectively. Brain computed tomography angiography (CTA) was the initial imaging study and acute stroke magnetic resonance angiography (MRA) followed after finished IV-tPA. Early recanalization rate was evaluated by acute stroke MRA within 2 hours after the IV-tPA. In 167 patients undertook IV-tPA only and 133 non-recanalized patients by IV-tPA, additional IA-Tx tried (IV-tPA + IA-Tx group). And 131 patients, non-recanalized by IV-tPA (IV-tPA group) additional IA-Tx recommend and tried according to the patient condition and compliance. RESULTS: Early recanalization rate of LVO after IV-tPA was 12.0% (36/300). In recanalized patients, favorable outcome (modified Rankin Scale, 0-2) was 69.4% (25/36) while it was 32.1% (42/131, p<0.001) in non-recanalized patients. Among 133 patients, nonrecanalized after intravenous recombinant tissue plasminogen activator and undertook additional IA-Tx, the clinical outcome was better than not undertaken additional IA-Tx (favorable outcome was 42.9% vs. 32.1%, p=0.046). Analysis according to the perfusion/diffusion (P/D)-mismatching or not, in patient with IV-tPA with IA-Tx (133 patients), favorable outcome was higher in P/ D-mismatching patient (52/104; 50.0%) than P/D-matching patients (5/29; 17.2%; p=0.001). Which treatment tired, P/D-mismatching was favored in clinical outcome (iv-tPA only, p=0.008 and IV-tPA with IA-Tx, p=0.001). CONCLUSION: The P/D-mismatching influences on the recanalization and clinical outcomes of IV-tPA and IA-Tx. The authors would like to propose that we had better prepare IA-Tx when LVO is diagnosed on initial diagnostic imaging. Furthermore, if the patient shows P/D-mismatching on MRA after IV-tPA, additional IA-Tx improves treatment results and lessen the futile recanalization.
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Low-dimensional Cu(I)-based metal halide materials are gaining attention due to their low toxicity, high stability and unique luminescence mechanism, which is mediated by self-trapped excitons (STEs). Among them, Cs5 Cu3 Cl6 I2 , which emits blue light, is a promising candidate for applications as a next-generation blue-emitting material. In this article, an optimized colloidal process to synthesize uniform Cs5 Cu3 Cl6 I2 nanocrystals (NCs) with a superior quantum yield (QY) is proposed. In addition, precise control of the synthesis parameters, enabling anisotropic growth and emission wavelength shifting is demonstrated. The synthesized Cs5 Cu3 Cl6 I2 NCs have an excellent photoluminescence (PL) retention rate, even at high temperature, and exhibit high stability over multiple heating-cooling cycles under ambient conditions. Moreover, under 850-nm femtosecond laser irradiation, the NCs exhibit three-photon absorption (3PA)-induced PL, highlighting the possibility of utilizing their nonlinear optical properties. Such thermally stable and highly luminescent Cs5 Cu3 Cl6 I2 NCs with nonlinear optical properties overcome the limitations of conventional blue-emitting nanomaterials. These findings provide insights into the mechanism of the colloidal synthesis of Cs5 Cu3 Cl6 I2 NCs and a foundation for further research.
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Quantitative determination and in situ monitoring of molecular chirality at extremely low concentrations is still challenging with simple optics because of the molecular-scale mismatch with the incident light wavelength. Advances in spectroscopy1-4 and nanophotonics have successfully lowered the detection limit in enantioselective sensing, as it can bring the microscopic chiral characteristics of molecules into the macroscopic scale5-7 or squeeze the chiral light into the subwavelength scale8-17. Conventional nanophotonic approaches depend mainly on the optical helicity density8,9 by localized resonances within an individual structure, such as localized surface plasmon resonances (LSPRs)10-16 or dielectric Mie resonances17. These approaches use the local chiral hotspots in the immediate vicinity of the structure, whereas the handedness of these hotspots varies spatially. As such, these localized resonance modes tend to be error-prone to the stochasticity of the target molecular orientations, vibrations and local concentrations18,19. Here we identified enantioselective characteristics of collective resonances (CRs)20 arising from assembled 2D crystals of isotropic, 432-symmetric chiral gold nanoparticles (helicoids)21,22. The CRs exhibit a strong and uniform chiral near field over a large volume above the 2D crystal plane, resulting from the collectively spinning, optically induced dipoles at each helicoid. Thus, energy redistribution by molecular back action on the chiral near field shifts the CRs in opposite directions, depending on the handedness of the analyte, maximizing the modulation of the collective circular dichroism (CD).
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Highly fluorescent blue emitters with high color purity are of great significance for optical applications. Herein, a series of planarized B,N-diarylated benzonaphthoazaborine compounds, namely, BzNp (1), BuBzNp (2), Bu2BzNp (3), Bu2BzMeNp (4), and Bu2BzBuNp (5), where electron-donating t Bu and Me groups are differently introduced into the B-Ph, N-Ph, or benzoazaborine rings, are prepared and characterized. All compounds exhibit low-energy absorptions (λ abs = 462-467 nm) and emissions (λ PL = 472-478 nm) remarkably red-shifted compared with those found for the pristine dibenzoazaborine compound (404 and 415 nm, respectively). Although the expansion of π-conjugation in the azaborine ring by replacing one phenyl ring with a naphthyl ring is mainly responsible for the redshifts, the emission is also fine-tuned by attached alkyl groups, which have a greater impact on the B-centered LUMO level at the azaborine ring than at the B-Ph ring. The bandgap control and emission tuning are further supported by electrochemical and theoretical studies. Notably, blue to sky-blue fluorescence of all compounds exhibits unitary photoluminescence quantum yields, narrow full width at half maximum values (â¼20 nm), and small Stokes shifts (â¼11 nm), indicating strong emissions with high color purity.
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Highly uniform Cu micropillars were electrodeposited on a Cu seed layer in a micropatterned photoresist in the presence of binary levelers containing pyrrolidine and pyridine functional groups. The adsorption behaviors of binary levelers, i.e., 3-hydroxy-6-(tert-butyl)pyridine and pyridinium tribromide in an electroplating bath were investigated by chronopotentiometry with sequential injection of levelers and linear sweep voltammetry with a rotating disk electrode. From electrochemical analysis, pyridinium tribromide composed of a positively charged pyridine ring was strongly adsorbed on the Cu seed surface, relative to 3-hydroxy-6-(tert-butyl)pyridine. Additional microscopy, surface roughness, and nitrogen concentration analyses revealed that the binary levelers were preferentially adsorbed on the center and the edge region of the Cu seed, resulting in a uniform Cu pillar profile. The possible mechanism of highly uniform Cu pillar deposition was discussed in terms of the adsorption behaviors of the levelers dependent on their molecular structures.
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Survivors of disasters can be expected to form meaningful perspectives on their experiences that shape their trajectories of recovery; thus, these perspectives are important to study. If humans are naturally compelled to create meaning from traumatic experiences, the creation of meaning should be evident in survivors' discussion of the effects of the disaster in their lives. Therefore, the purpose of this study of highly trauma-exposed disaster survivors was to identify meaningful aspects or outcomes of their disaster experiences in their perspectives. This study examined a random sample (N=182) of survivors of the Oklahoma City bombing six months after the disaster using open-ended questions. Text responses (N=650) were compiled, themes identified by multiple coders, responses coded into the themes, interrater reliability established, and the themes were then interpreted. Six themes were identified and grouped into three general categories: personal aspirations (reprioritizing life and altruism and self-improvement), connection with others (a freestanding category/theme), and making meaning (appreciation for life, religion and spirituality, and contemplating life, death, and humanity), which contained the majority of the responses. The findings from this study affirm the human need to make meaning from the experience of a traumatic disaster and suggest the potential relevance to survivors' recovery of therapies based on the creation of meaning and the promotion of positive growth.
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This study compared perspectives of highly trauma-exposed Oklahoma City bombing survivors (N=141) with and without PTSD. Survivors' responses to questions about the effects of the bombing on their perspectives were hand-recorded and transcribed, six themes identified, and interrater reliability established. Both diagnostic groups (with and without PTSD) expressed greater appreciation for life, greater concern with human vulnerability and mortality, and positive changes in religion/spirituality as consequences of the bombing. Survivors with PTSD also expressed negative religious/spiritual changes and substantive gains in self-confidence. Results indicate that disaster survivors may experience profound changes in their perspectives with ramifications for their mental health.
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Salt contents in soil or groundwater are one of the primary indicators to evaluate contamination levels. Electrical conductivity (EC) or salinity information from the conventional laboratory analysis is typically inefficient in delineating contamination. This study investigated a rapid determination of ionic contents in water through the combination of Ultraviolet Spectroscopy (UVS) and Electrochemical Impedance Spectroscopy (EIS), and the application of convolutional neural network (CNN). Various aqueous salt samples were prepared with Ca2+, K+, Na+, Cl-, Br-, SO42-, and HCO3- ions. Firstly, their spectral data obtained from UVS and EIS were analyzed. The spectral analysis showed that the data fusion of both spectroscopies provided more evidence to distinguish the ionic contents, consequently enhancing prediction performance of CNN. In turn, the fused spectra were handled with CNN to predict ionic contents. The result suggested the validity of the proposed method in detecting ionic contents by showing 48.6 mmol/kg RMSE and 0.95 R2 between actual and predicted ionic concentrations, which outperformed Partial Least Squares Regression (PLSR) and Random Forest. The detection of ionic contents beyond EC or salinity is advantageous since it provides more information on the soil and water contamination, and it facilitates tracking the contaminant sources. The proposed method has the potential to become more accurate with increased datasets and further optimization of CNN, which will further improve the practicability.
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Redes Neurales de la Computación , Agua , Iones , Suelo/química , Análisis Espectral/métodosRESUMEN
OBJECTIVE: Since the outbreak of the coronavirus disease 2019 (COVID-19) pandemic, neurointerventionists have been increasingly concerned regarding the prevention of infection and time delay in performing emergency thrombectomy procedures in patients with acute stroke. This study aimed to analyze the effects of changes in mechanical thrombectomy protocol before and after the COVID-19 pandemic on procedure time and patient outcomes and to identify factors that significantly impact procedure time. METHODS: The last-normal-to-door, first-abnormal-to-door, door-to-imaging, door-to-puncture, and puncture-to-recanalization times of 88 patients (45 treated with conventional pre-COVID-19 protocol and 43 with COVID-19 protection protocol) were retrospectively analyzed. The recanalization time, success rate of mechanical thrombectomy, and modified Rankin score of patients at discharge were assessed. A multivariate analysis was conducted to identify variables that significantly influenced the time delay in the door-to-puncture time and total procedure time. RESULTS: The door-to-imaging time significantly increased under the COVID-19 protection protocol (p=0.0257) compared to that with the conventional pre-COVID-19 protocol. This increase was even more pronounced in patients who were suspected to be COVID-19-positive than in those who were negative. The door-to-puncture time showed no statistical difference between the conventional and COVID-19 protocol groups (p=0.5042). However, in the multivariate analysis, the last-normal-to-door time and door-to-imaging time were shown to affect the door-to-puncture time (p=0.0068 and 0.0097). The total procedure time was affected by the occlusion site, last-normal-to-door time, door-to-imaging time, and type of anesthesia (p=0.0001, 0.0231, 0.0103, and 0.0207, respectively). CONCLUSION: The COVID-19 protection protocol significantly impacted the door-to-imaging time. Shortening the door-to-imaging time and performing the procedure under local anesthesia, if possible, may be required to reduce the door-to-puncture and doorto- recanalization times. The effect of various aspects of the protection protocol on emergency thrombectomy should be further studied.
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OBJECTIVE: Research is needed on disaster-affected workplaces, particularly on employee job satisfaction and performance, to inform workplace responses promoting employee postdisaster adjustment and wellbeing. METHODS: Quantitative and qualitative data were collected from a volunteer sample of 255 employees of eight workplaces affected by the 9/11 attacks on New York City's World Trade Center nearly 3âyears post disaster. RESULTS: The effects of 9/11 on both job satisfaction and job performance were more negative than positive, especially for the Ground Zero employees. Effects on job satisfaction and job performance were generally congruent. Workplace responses focused on individual needs were perceived as positive and those focused on workplace needs as negative. CONCLUSIONS: Workplace responses focused on business improvement intended to improve workplace performance may not have the desired effect and may reduce employee job satisfaction and performance.
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Satisfacción en el Trabajo , Lugar de Trabajo , Humanos , Ciudad de Nueva York , Satisfacción PersonalRESUMEN
In this study, we demonstrate a new approach to easily prepare spinel Co3O4 nanoparticles (s-Co3O4 NPs) in the gram-scale from the cathode of spent lithium ion batteries (SLIBs) by the alkali leaching of hexaamminecobalt(III) complex ions. As-obtained intermediate and final products were characterized with powder X-ray diffraction (PXRD), Ultraviolet-Visible (UV-Vis), Fourier transform infrared (FTIR), and Transmission electron microscopy (TEM). Additionally, the synthesized s-Co3O4 NPs showed better electrocatalytic properties toward the oxygen evolution reaction (OER) in comparison to previously reported Co3O4 NPs and nanowires, which could be due to the more exposed electrocatalytic active sites on the s-Co3O4 NPs. Moreover, the electrocatalytic activity of the s-Co3O4 NPs was comparable to the previously reported RuO2 catalysts. By taking advantage of the proposed recycling route, we would expect that various valuable transition metal oxide NPs could be prepared from SLIBs.
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Aim: Postoperative delirium (POD) is associated with increased morbidity and is poorly understood. The aim of this review was to identify putative mechanisms through re-analysis of randomized trials on treatment or prevention of POD. Materials & methods: A systematic review was performed to identify systematic reviews of treatments for POD. Constituent randomized controlled trials were identified, and interventions were grouped according to hypothesized mechanisms of action. Effects were meta-analyzed by hypothesized mechanism and timing of intervention. Results: A total of 116 randomized controlled trials described 47 individual interventions for POD, with nine mechanisms identified. The largest effects were observed for postoperative inflammation reduction, and preoperative reinforcement of sleep-wake cycle. Conclusion: This approach identifies treatments focused on mechanisms of action that may be front runners for future trials and interventions.
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Delirio , Complicaciones Posoperatorias , Delirio/prevención & control , Humanos , Revisiones Sistemáticas como AsuntoRESUMEN
The design of robust boron acceptors plays a key role in the development of boron-based thermally activated delayed fluorescence (TADF) emitters for the realization of efficient and stable blue organic light-emitting diodes (OLEDs). Herein, we report a set of donor (D)-acceptor (A)-type blue TADF compounds (1-3) comprising triply bridged triarylboryl acceptors, the so-called B-heterotriangulenes, which differ depending on the identity of one of the bridging groups: methylene (1), dimethylmethylene (2), or oxo (3). The X-ray crystal structures of 2 and 3 reveal a highly twisted D-A connectivity and a completely planar geometry for the B-heterotriangulene rings. All compounds exhibit blue emissions with the unitary photoluminescence quantum yields and small singlet-triplet energy splitting (<0.1 eV) in their doped host films. The compounds exhibit a fast reverse intersystem crossing rate (kRISC ≈ 106 s-1) with short-lived delayed fluorescence (τd ≈ 2 µs), which is found to be promoted by the strong spin-orbit coupling between the local triplet excited state (3LE, T2) and singlet (S1) states. Using compounds 1-3 as the emitters, highly efficient blue TADF-OLEDs are realized. The devices based on the emitters with B-heterotriangulenes exhibit better performances than the device incorporating a singly bridged reference emitter over the whole luminance range. Notably, the device based on the fully dimethylmethylene-bridged emitter (2) achieves the highest maximum external quantum efficiency (EQE) of 28.2% and the lowest efficiency roll-off, maintaining a high EQE value of 21.2% at 1000 cd/m2.