Asymmetric three-component 1,2-oxytrifluoromethylations of styrenes were explored by using N-oxyphthalimide (NOPI) as the resulting benzylic radical anchor after cross-coupling by a CF3 radical under ...the catalyses of chiral N-salicylidene-derived oxovanadium(V) complexes. Among the 15 different solvents and 15 different catalysts examined, the best scenarios were in i-PrOH with C3-tert-butyl or C3-fluoro-/2,5-dimethylphenyl-substituted vanadyl catalysts that led to the corresponding complementary S and R products in up to 88% yields and 87/86% ees, respectively, with further enrichment to at least 94% ee after a single recrystallization. The ccontrol α-(2-phenylcyclopropyl)styrene was tested to prove the asymmetric event involving the benzylic radical species. DFT computations showed that the SOMO of the benzylic radical is placed in a way to orient the CF3CH2 group away from the tert-butyl group in the salicylidene-l-tert-butylglycinate template by interacting with the N-oxygen atom of NOPI bound to the vanadium center with a bimolecular homolytic substitution (SH2) type mechanism. The enantioselectivity profile was dominated by several noncovalent interactions between the intermediary vanadium(NOPI) complex and the resulting benzylic radical.
An ultralow program/erase voltage (<inline-formula> <tex-math notation="LaTeX">\vert {V}_{\textit {P/E}}\vert = 4 </tex-math></inline-formula> V) is demonstrated by using an ...antiferroelectric-ferroelectric field-effect transistor (AFE-FE-FET) through a multipeak coercive <inline-formula> <tex-math notation="LaTeX">{E} </tex-math></inline-formula>-field (<inline-formula> <tex-math notation="LaTeX">{E}_{C} </tex-math></inline-formula>) concept for a four-level stable state with outstanding endurance (>10 5 cycles) and data retention (>10 4 s at 65 °C). The mixture of ferroelectric (FE) and AFE domains can provide stable multistate and data storage with zero bias for multilevel cell (MLC) applications. HfZrO 2 (HZO) with AFE-FE assembles an orthorhombic/tetragonal (o/t) phase composition and is achieved by Zr modulation in an HZO system. MLC characteristics not only improve high-density nonvolatile memory (NVM) but are also beneficial to neuromorphic device applications.
Previous studies have consistently reported a positive effect of acute exercise on cognition, particularly on executive function. However, most studies have focused on aerobic and resistant forms of ...exercise. The purpose of this study was to compare the effect of 'open-skill' with 'closed-skill' exercise (defined in terms of the predictability of the performing environment) on brain-derived neurotrophic factor (BDNF) production and task switching performance. Twenty young adult males participated in both closed (running) and open (badminton) skill exercise sessions in a counterbalanced order on separate days. The exercise sessions consisted of 5 min of warm up exercises followed by 30 min of running or badminton. The exercise intensity was set at 60% (±5%) of the heart rate reserve level (HRR) with HR being monitored by a wireless heart rate monitor. Blood samples were taken and participation in a task-switching paradigm occurred before and after each exercise session. Results showed no differences in serum BDNF or task-switching performance at the pre-test stage, however, badminton exercise resulted in significantly higher serum BDNF levels (a proxy for levels of BDNF in the brain) and near significant smaller global switching costs relative to running. This study has provided preliminary evidence in support the relative benefits of open-skills exercises on BDNF and executive function.
Unresectable esophageal cancer harbors high mortality despite chemoradiotherapy. Better patient selection for more personalized management may result in better treatment outcomes. We presume the ...ratio of maximum standardized uptake value (SUV) of metastatic lymph nodes to primary tumor (NTR) in 2-deoxy-2-18Ffluoro-D-glucose positron emission tomography/computed tomography (FDG PET/CT) may provide prognostic information and further stratification of these patients.
The patients with non-metastatic and unresectable esophageal squamous cell carcinoma (SCC) receiving FDG PET/CT staging and treated by chemoradiotherapy were retrospectively reviewed. Receiver operating characteristic (ROC) analysis was performed to determine the optimal cut-off value for NTR. Kaplan-Meier method and Cox regression model were used for survival analyses and multivariable analyses, respectively.
From 2010 to 2016, 96 eligible patients were analyzed. The median follow-up time was 10.2 months (range 1.6 to 83.6 months). Using ROC analysis, the best NTR cut-off value was 0.46 for prediction of distant metastasis. The median distant metastasis-free survival (DMFS) was significantly lower in the high-NTR group (9.5 vs. 22.2 months, p = 0.002) and median overall survival (OS) (9.5 vs. 11.6 months, p = 0.013) was also significantly worse. Multivariable analysis revealed that NTR was an independent prognostic factor for DMFS (hazard ratio HR 1.81, p = 0.023) and OS (HR 1.77, p = 0.014).
High pretreatment NTR predicts worse treatment outcomes and could be an easy-to-use and helpful prognostic factor to provide more personalized treatment for patients with non-metastatic and unresectable esophageal SCC.
The current clinical workflow for esophageal gross tumor volume (GTV) contouring relies on manual delineation with high labor costs and inter-user variability.
To validate the clinical applicability ...of a deep learning multimodality esophageal GTV contouring model, developed at one institution whereas tested at multiple institutions.
We collected 606 patients with esophageal cancer retrospectively from four institutions. Among them, 252 patients from institution 1 contained both a treatment planning CT (pCT) and a pair of diagnostic FDG-PET/CT; 354 patients from three other institutions had only pCT scans under different staging protocols or lacking PET scanners. A two-streamed deep learning model for GTV segmentation was developed using pCT and PET/CT scans of a subset (148 patients) from institution 1. This built model had the flexibility of segmenting GTVs
only pCT or pCT+PET/CT combined when available. For independent evaluation, the remaining 104 patients from institution 1 behaved as an unseen internal testing, and 354 patients from the other three institutions were used for external testing. Degrees of manual revision were further evaluated by human experts to assess the contour-editing effort. Furthermore, the deep model's performance was compared against four radiation oncologists in a multi-user study using 20 randomly chosen external patients. Contouring accuracy and time were recorded for the pre- and post-deep learning-assisted delineation process.
Aim The objective of this study was to investigate the mechanisms underlying the deficit in visuospatial working memory (VSWM) seen in children with developmental coordination disorder (DCD) and to ...compare brain activity while performing a VSWM task in children with DCD and typically developing children.
Method Behavioural performance and event‐related potentials (ERPs) were recorded in 24 children (12 males, 12 females; mean age 139mo, SD 4mo) with DCD (as determined by a score <5th centile on the Movement Assessment Battery for Children – Second Edition) and in 30 age‐ and sex‐matched typically developing children (15 males; 15 females; mean age 140mo, SD 5mo) recruited from local schools, while performing one spatial non‐delay and two time‐delayed spatial memory tasks.
Results Compared with typically developing children, children with DCD exhibited longer reaction times (p = 0.022; partial η2=0.10) and lower accuracy rates (p < 0.001; partial η2 = 0.35) on the two spatial memory tasks. Electrophysiological indices also showed distinct modulatory effects, with children with DCD exhibiting smaller P3 (p < 0.001; partial η2 = 0.26) and positive slow wave (pSW; p = 0.003; partial η2 = 0.16) amplitude and a smaller area under the curve of P3 and pSW components (p = 0.002; partial η2 = 0.17).
Interpretation The combined analysis of behavioural performance and ERP data suggests that children with DCD have deficits of visuospatial working memory owing to fewer resources being allocated to comparison of spatial locations, less effort allotted to the response selection, and less neural processing employed during the retrieval process phase.
This article is commented on by Alloway on pages 1075–1076 of this issue.
The prognosis of patients with resected esophageal squamous cell carcinoma after neoadjuvant chemoradiotherapy is particularly poor in those who were staged as ypT3/T4 and/or ypN+. This study ...investigated whether adjuvant chemoradiotherapy was associated with improved clinical outcomes in these patients.
we identified patients with esophageal squamous cell carcinoma who were staged as ypT3/T4 and/or ypN+ after being treated with neoadjuvant chemoradiotherapy followed by esophagectomy between the years 2013 and 2019. Patients were divided into two groups based on whether they received adjuvant chemoradiotherapy. The Kaplan-Meier method and Cox regression modeling were performed for survival analyses and multivariable analysis, respectively.
76 eligible patients were included in the analyses. The median follow-up for the study cohort was 43.4 months. On Kaplan-Meier analyses of the overall population, adjuvant chemoradiotherapy was associated with significantly improved median overall survival (31.7 months vs. 16.3 months,
= 0.036). On Kaplan-Meier analyses of the 35 matched pairs generated by propensity score matching, adjuvant chemoradiotherapy was associated with significantly longer median overall survival (31.7 months vs. 14.3 months;
= 0.004) and median recurrence-free survival (18.9 months vs. 11.7 months;
= 0.020). In multivariable analysis, adjuvant chemoradiotherapy was independently associated with a 60% reduction in mortality (
= 0.003) and a 48% reduction in risk of recurrence (
= 0.035) after adjusting for putative confounders. In addition, microscopic positive resection margin and Mandard tumor regression grade 3-4 were independently associated with increased mortality and risk of recurrence. While a greater number of lymph nodes dissected was independently associated with significantly improved overall survival, the number of positive lymph nodes was independently associated with significantly worse overall survival and a trend (
= 0.058) towards worse recurrence-free survival.
This study demonstrated that adjuvant CRT was independently associated with a significantly improved survival and lower risk of recurrence than observation in esophageal squamous cell carcinoma patients staged as ypT3 and/or ypN+ after receiving neoadjuvant chemoradiotherapy and radical surgery. The results of this study have implications for the design of future clinical trials and may improve treatment outcomes of patients in this setting who cannot afford or are without access to adjuvant nivolumab.
The continuous fractional Fourier transform (FRFT) performs a spectrum rotation of signal in the time-frequency plane, and it becomes an important tool for time-varying signal analysis. A discrete ...fractional Fourier transform has been developed by Santhanam and McClellan (see ibid., vol.42, p.994-98, 1996) but its results do not match those of the corresponding continuous fractional Fourier transforms. We propose a new discrete fractional Fourier transform (DFRFT). The new DFRFT has DFT Hermite eigenvectors and retains the eigenvalue-eigenfunction relation as a continous FRFT. To obtain DFT Hermite eigenvectors, two orthogonal projection methods are introduced. Thus, the new DFRFT will provide similar transform and rotational properties as those of continuous fractional Fourier transforms. Moreover, the relationship between FRFT and the proposed DFRFT has been established in the same way as the conventional DFT-to-continuous-Fourier transform.
Sustamine™ (SUS) is a dipeptide composed of alanine and glutamine (AlaGln). Glutamine has been suggested to increase muscle protein accretion; however, the underlying molecular mechanisms of ...glutamine on muscle protein metabolism following resistance exercise have not been fully addressed. In the present study, 2-month-old rats climbed a ladder 10 times with a weight equal to 75 % of their body mass attached at the tail. Rats were then orally administered one of four solutions: placebo (PLA-glycine = 0.52 g/kg), whey protein (WP = 0.4 g/kg), low dose of SUS (LSUS = 0.1 g/kg), or high dose of SUS (HSUS = 0.5 g/kg). An additional group of sedentary (SED) rats was intubated with glycine (0.52 g/kg) at the same time as the ladder-climbing rats. Blood samples were collected immediately after exercise and at either 20 or 40 min after recovery. The flexor hallucis longus (FHL), a muscle used for climbing, was excised at 20 or 40 min post exercise and analyzed for proteins regulating protein synthesis and degradation. All supplements elevated the phosphorylation of FOXO3A above SED at 20 min post exercise, but only the SUS supplements significantly reduced the phosphorylation of AMPK and NF-kB p65. SUS supplements had no effect on mTOR signaling, but WP supplementation yielded a greater phosphorylation of mTOR, p70S6k, and rpS6 compared with PLA at 20 min post exercise. However, by 40 min post exercise, phosphorylation of mTOR and rpS6 in PLA had risen to levels not different than WP. These results suggest that SUS blocks the activation of intracellular signals for MPB, whereas WP accelerates mRNA translation.
The increased importance of mobile photography created a need for fast and performant RAW image processing pipelines capable of producing good visual results in spite of the mobile camera sensor ...limitations. While deep learning-based approaches can efficiently solve this problem, their computational requirements usually remain too large for high-resolution on-device image processing. To address this limitation, we propose a novel PyNET-V2 Mobile CNN architecture designed specifically for edge devices, being able to process RAW 12MP photos directly on mobile phones under 1.5 second and producing high perceptual photo quality. To train and to evaluate the performance of the proposed solution, we use the real-world Fujifilm UltraISP dataset consisting on thousands of RAW-RGB image pairs captured with a professional medium-format 102MP Fujifilm camera and a popular Sony mobile camera sensor. The results demonstrate that the PyNET-V2 Mobile model can substantially surpass the quality of tradition ISP pipelines, while outperforming the previously introduced neural network-based solutions designed for fast image processing. Furthermore, we show that the proposed architecture is also compatible with the latest mobile AI accelerators such as NPUs or APUs that can be used to further reduce the latency of the model to as little as 0.5 second. The dataset, code and pre-trained models used in this paper are available on the project website: https://github.com/gmalivenko/PyNET-v2
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