bluuebunny/crossref_metadata_2025_split huggingface dataset:
National Comprehensive Cancer Network Guideline Recommendations of Cancer Drugs With Accelerated Approval
Authors: Cliff Edward R. Scheffer , Rome Rachel S. , Kesselheim Aaron S. , Rome Benjamin N. 
Published: November 2023

ImportanceMany cancer drugs are approved under the US Food and Drug Administration (FDA) accelerated approval pathway based on preliminary evidence. It is unclear how this limited evidence is integrated into the National Comprehensive Cancer Network (NCCN) guidelines, which are common references for clinicians and are used by public and private payers to determine reimbursement for oncology treatments.ObjectiveTo analyze the NCCN guidelines’ assessments for cancer drug indications that received FDA accelerated approval compared with cancer drug indications that received FDA regular approval.Design, Setting, and ParticipantsThis cross-sectional study analyzes FDA-approved indications for cancer drugs that were granted accelerated approval from program inception in 1992 to June 30, 2022. For each drug, the FDA-approved labeling was reviewed to identify all indications. All analyses were performed at the drug-indication level.ExposureThe exposure was FDA regulatory status as of October 2022, including regular approval, accelerated approval, accelerated approval converted to regular approval, and withdrawn accelerated approval.Main Outcomes and MeasuresThe level of evidence and consensus (category 1, 2A, 2B, and 3) and treatment preference (preferred, alternative preferred, other recommended, and useful in certain circumstances) ratings assigned by NCCN committees as of February 2023.ResultsA total of 315 oncology indications for 100 drugs were analyzed. These indications included 156 (50%) with regular approval, 60 (38%) with accelerated approval, 78 (49%) with accelerated approval that was converted to regular approval, and 21 (13%) with withdrawn accelerated approvals. Among all indications, 105 (33%) were rated by the NCCN as having category 1 evidence, 185 (59%) with category 2A, 6 (2%) with category 2B, and 2 (1%) with category 3 evidence. Compared with indications with regular approval, those with accelerated approval were less frequently assigned category 1 evidence (47% vs 3%; P &amp;lt; .001) and were less often listed as preferred treatment options (58% vs 40%; P = .008). Among the 21 withdrawn accelerated approval indications, 8 (38%) remained in the NCCN guidelines, with most having level 2A evidence ratings.Conclusions and RelevanceThis study found that cancer drug indications with accelerated approval were less likely to be assigned high-level evidence ratings and preferred status in the NCCN guidelines compared with indications with regular approval; most accelerated and regular approval drugs had low-quality evidence ratings but high levels of consensus among oncologists on NCCN committees. Greater clarity on the thresholds and definitions of evidence levels would make the NCCN guidelines more useful to clinicians, patients, and payers.
Comparison of baseline drifts using three reflector blocks versus using a single reflector block for the calibration of wall‐mounted Respiratory Gating for Scanner (RGSC) camera integrated with a CT
Authors: Liu Bei , Shi Chengyu , Prakash Maneesha , Gonzalez Bryan , Kassardjian Ari , Kim Ji , Mandelin Paul , Williams Terence , Liu An 
Published: November 2023

AbstractBackgroundThe calibration of the Respiratory Gating for SCanner (RGSC) system is critical to achieve better and more stable accuracy. The current procedure for a wall‐mounted RGSC system has a relatively large residual error.PurposeTo compare the baseline drifts in the image acquisition of DIBH using three reflector blocks versus using a single reflector block in the calibration of a wall‐mounted RGSC camera system.Materials and methodsVarian provides a calibration plate with three rows of calibration points: each row is separated by 15 cm longitudinally and by 10 cm laterally. In Varian's single‐block calibration method, the reflector block was first placed on the center point of the calibration plate and aligned with the scanner isocenter. The calibration took a picture of the block, then placed the block on the other eight points sequentially. In the proposed three‐block method, we placed three reflector blocks on the center row, with the center block aligned with the isocenter, and we took a picture of the center block by manually blocking the other two blocks in calibration. By moving the couch longitudinally in or out 15 cm, the calibration goes through all nine points. Monte Carlo simulation was done using Matlab to analyze the calibration matrix eigenvalue characteristics.ResultsFor a typical scan length of 40 cm of DIBH, the residual baseline drift in simulated DIBH is 0.02 ± 0.03 versus 0.30 ± 0.12 cm for three‐block calibration and single‐block calibration, respectively. To achieve 0.5 mm tolerance for the eigenvalue, the laser and reflector box should be within ±3 mm uncertainties based on the eigenvalue simulation.ConclusionThree‐block calibration method effectively removes baseline drift caused by couch movement in DIBH/4D CT scan for the wall‐mounted camera while the single‐block calibration method still has significant residual baseline drift.
Insights Into Curie‐Temperature and Phase Formation of Ferroelectric Hf1−xZrxO2with Oxygen Defects from a Leveled Energy Landscape
Authors: Azevedo Antunes Luis , Ganser Richard , Schroeder Uwe , Mikolajick Thomas , Kersch Alfred 
Published: November 2023

AbstractThe phase composition of HZO thin films is critical for the ferroelectric and electrical properties of the films and the devices they are integrated into. Optimization is a major challenge since the phase formation depends significantly on many influencing variables that are only partially understood so far. The Curie temperature is identified as an important parameter for understanding the behavior, since it depends sensitively on Zr content, the density of oxygen‐related defects, layer thickness, and external stress. A two‐step process, phase formation by pure kinetic transformation followed by nucleation, is proposed for phase formation. This is necessary because nucleation theory alone cannot explain the experimentally observed dependence on oxygen content. The classical nucleation model is modified at two crucial points. First, the polycrystalline structure is incorporated which allows the size effect to be implemented. Furthermore, the interface energies between the child and parent phase, which result from static ab initio calculations, are rescaled from dynamical effects. The resulting model is used to calculate the phase fractions during thermal processing. The results for the most important influencing variables are discussed and compared with experimental results. The causes of the undesired monoclinic phase are further analyzed.
Ring‐Opening Coupling Reaction of Cyclopropanols with Electrophilic Alkenes Enabled by Decatungstate as Photoredox Catalyst
Authors: Krech Anastasiya , Yakimchyk Viktoryia , Jarg Tatsiana , Kananovich Dzmitry , Ošeka Maksim 
Published: November 2023

AbstractWe introduce a methodology for the photocatalytic generation of β‐ketoalkyl radicals from tertiary cyclopropanols, utilizing tetrabutylammonium decatungstate (TBADT) as a photoredox catalyst. The application is demonstrated by the synthesis of distantly functionalized ketones via the redox‐neutral addition of the cyclopropanol‐derived β‐ketoalkyl radicals to the double bond of electrophilic olefins. The transformation occurs under ambient temperature conditions and is suitable for coupling a wide range of cyclopropanol and alkene substrates. This was demonstrated by the preparation of 33 ketone products with 35–92% yield. The method's preparative robustness has been validated through upscaled preparations conducted under continuous flow conditions. Mechanistic investigations support the role of TBADT as a photoredox catalyst, which facilitates the single electron oxidation of cyclopropanols, followed by the electron transfer from the reduced form of decatungstate to the electrophilic double bond of alkene. Moreover, we found that electron‐rich aromatic cyclopropanols and electron‐deficient olefins form photoactive electron donor‐acceptor (EDA) complexes. This property allows the reaction to proceed under UV light irradiation via the photoinduced charge transfer in the absence of the photocatalyst.
Visible Light Mediated Cyclization of Ynones for the Synthesis of 3‐Alkyl N‐Fused Indoles via Csp3−H Bond Functionalization
Authors: Xu Peidong , Han Weiwei , Zhou Yufeng , Xiong Heng‐Ying , Ni Shao‐Fei , Zhang Guangwu 
Published: November 2023

AbstractA visible‐light induced approach has enabled the synthesis of 3‐alkyl indole from ynones via Csp3−H bond functionalization. This protocol proceeded under base‐free conditions andat room temperature, providing a series of 3‐alkyl indole motifs in 39% to 90% yields (44 examples). Preliminary mechanistic studies suggest that a radical process should be involved in this transformation.
Implanted, Wireless, Self‐Powered Photodynamic Therapeutic Tablet Synergizes with Ferroptosis Inducer for Effective Cancer Treatment
Authors: Zou Pingjin , Lin Rui , Fang Zengyi , Chen Junyang , Guan Hongye , Yin Jie , Chang Zhiheng , Xing Lili , Lang Jinyi , Xue Xinyu , Chen Meihua 
Published: November 2023

AbstractThe effective and targeted treatment of resistant cancer cells presents a significant challenge. Targeting cell ferroptosis has shown remarkable efficacy against apoptosis‐resistant tumors due to their elevated iron metabolism and oxidative stress levels. However, various obstacles have limited its effectiveness. To overcome these challenges and enhance ferroptosis in cancer cells, we have developed a self‐powered photodynamic therapeutic tablet that integrates a ferroptosis inducer (FIN), imidazole ketone erastin (IKE). FINs augment the sensitivity of photodynamic therapy (PDT) by increasing oxidative stress and lipid peroxidation. Furthermore, they utilize the Fenton reaction to supplement oxygen, generating a greater amount of reactive oxygen species (ROS) during PDT. Additionally, PDT facilitates the release of iron ions from the labile iron pool (LIP), accelerating lipid peroxidation and inducing ferroptosis. In vitro and in vivo experiments have demonstrated a more than 85% tumor inhibition rate. This synergistic treatment approach not only addresses the limitations of inadequate penetration and tumor hypoxia associated with PDT but also reduces the required medication dosage. Its high efficiency and specificity towards targeted cells minimize adverse effects, presenting a novel approach to combat clinical resistance in cancer treatment.
Aging‐Resistant Precursor with Ultrawide Annealing Window for 24.08% Perovskite Solar Cells
Authors: Huang Zhangfeng , Ma Zhu , Deng Chen , Yu Tangjie , Li Guoming , Du Zhuowei , You Wei , Yang Junbo , Chen Yi , Li Yanlin , Hou Shanyue , Yang Qiang , Zhang Qian , Du Hao , Li Yixian , Shu Hui , Liu Qianyu , Peng Changtao , Huang Yuelong , Yu Jian , Lin Yuanhua , Sun Kuan , Long Wei 
Published: November 2023

AbstractPerovskite solar cells (PSCs) have attracted extensive attention in the photovoltaic field, with their highest power conversion efficiency (PCE) reaching 26%. However, the commercialization of PSCs is severely hindered by the instability of precursor solutions and the narrow annealing window for perovskite films. Here, 2,3,5‐trichlorobenzaldehyde (3Cl‐BZH) is introduced into the organic salt precursor solution to eliminate excess organic amines through Schiff‐base reactions, avoiding subsequent irreversible amine‐cation reaction of formamidine‐methylammonium (FA‐MA+) and improve the stability of the precursor solution. Meanwhile, the chemical interaction between C═O group of 3Cl‐BZH and formamidinium (FA+) in the perovskite precursor contributes to the slow release of organic ions, which reduces the reaction rate between organic salt and PbI2, retarding the crystallization of perovskite film. The PSCs with a conventional annealing process achieve a champion efficiency of 24.08%, which derives from the defect passivation effect of 3Cl‐BZH. The PSCs with an ultrawide annealing window of 240 h for wet perovskite film in the air still maintain an efficiency of 22.01%. The aging‐resistant precursor and ultrawide annealing window are beneficial for reproducible, efficient, and low‐cost PSCs, which brings great prospects for the commercialization of PSCs.
Evaluation of separation of seed mussels from macroalgae using chlorination
Authors: Skelton Bradley M. , Jeffs Andrew G. 
Published: November 2023

AbstractGrowing seed mussels (spat) to larger sizes in single‐seed nursery culture systems prior to seeding onto coastal mussel farms is an effective approach for greatly reducing costly spat losses during this stage of mussel aquaculture. However, the production of single‐seed mussel spat in nursery culture systems relies on first separating spat from the settlement substrata to which they are attached, whether spat are settled in a hatchery or gathered from the wild. This study sought to determine whether chlorination could be an effective approach for separating wild Greenshell mussel (Perna canaliculus) spat from beachcast macroalgal material (Kaitaia spat material) harvested from a beach in northern New Zealand. The results demonstrate that chlorination (i.e. in solutions of up to 0.625% sodium hypochlorite) is a highly effective approach for separating spat, resulting in the detachment of up to 94.6% in one treatment without increasing mortality relative to controls. The effectiveness of chlorination was modulated by spat density, with increasing spat densities, lowering rates of detachment. While chlorination is effective at separating small spat (i.e. successfully separating 72.4% of spat <750 μm in shell length) overall spat densities, further investigation is required to determine how to effectively separate larger spat (i.e. with chlorination only successfully separating 21.5% of spat >750 μm). The high survival (relative to the control treatments) also suggests that chlorine concentrations and exposure durations could be increased from those used in this study. These results demonstrate that chlorination can be used to separate spat from substrate prior to their transfer to nursery systems for ongrowing, paving the way for such approaches for reducing spat losses to be integrated into the aquaculture production cycle.
Ecopsychosocial accompaniment: Cocreating with humility
Authors: Watkins Mary 
Published: November 2023

AbstractWhen Seymour Sarason, the founder of American community psychology, looked back on his life and work, he singled out the importance of personal humility and of developing collaborative learning relationships. He worried that humility was too lacking in psychology. To cultivate humility, we need to engage in an ongoing practice of critical self‐ and group‐examination that enables us to understand more fully the effects of our positionalities, historical, and cultural contexts. Alongside this we need to try to understand the ecopsychosocial and historical contexts of those we have been invited to accompany. For those who are European descended, this requires a deepening realization of how we, as W. E. B. Du Bois would say, have been and are a “problem.” Unawares, we have saturated psychology with our own cultural perspectives and ways of being. “White” people require their own pedagogy to become more conscious of their standpoints and to redress the harms created by their group. Our task is not to evangelize psychological theories and practices born from within our own particular cultural perspective, but to learn from the cultural workers and community members in the group we are working with. We must ask of ourselves questions that enable us to understand the broader historical, social, and ecological context of the issues that are presenting. To indicate this, I preface the term “accompaniment” with the adjective “ecopsychosocial.” Ecopsychosocial accompaniment requires humility. It is humility that opens the door to being able to imagine and desire together, to cocreate, and cosustain the kinds of decolonial spaces, places, and ways of working and living with one another that are so desperately needed.
Validity and reliability of Meu Educativo®: A new tool to assess fundamental movement skills in school‐aged children
Authors: Garbeloto Fernando , Pereira Sara , Tani Go , Chaput Jean‐Philippe , Stodden David F. , Garganta Rui , Hedeker Donald , Katzmarzyk Peter T. , Maia José 
Published: November 2023

AbstractObjectivesThere is evidence showing that children's proficiency in fundamental movement skills (FMS) is positively related to weight status, physical activity, fitness levels, cognitive development, as well as academic performance. Yet, the feasibility of FMS assessment is challenging, especially with relatively large samples of children. This article presents a new tool named Meu Educativo® to assess children's FMS levels, including its validity and reliability.MethodsWe relied on the validity evidence approach based on test content to develop the FMS assessment checklist and the rating system with a team of experts. In this article, we used five FMS (stationary dribbling, kick, overhand throw, catch the ball, and underhand roll). Further, we conducted a series of reliability studies and used percent agreement and Cohen's kappa (κ) as statistics.ResultsExperts agreed highly on the checklist's components in the five FMS. Inter‐rater reliability ranged from 0.63 for stationary dribbling to 0.93 for overhand throw, and the intra‐rater reliability ranged from 0.46 to 0.94.ConclusionBased on the first results, Meu Educativo® was not only easy to use, but was also a reliable tool for FMS assessments. Notwithstanding the need for future studies, Meu Educativo® is a new tool that can be used by teachers, coaches, and motor development specialists dealing with school‐aged children and researchers working with large samples.
Photoswitchable Enantioselective and Helix‐Sense Controlled Living Polymerization
Authors: Zhou Li , He Kai , Kang Shu‐Ming , Zhou Xing‐Yu , Zou Hui , Liu Na , Wu Zong‐Quan 
Published: November 2023

AbstractA pair of enantiomeric photoswitchable PdII catalysts, alkyne‐PdII/LR−azo and alkyne‐PdII/LS−azo, were prepared via the coordination of alkyne‐PdII and azobenzene‐modified phosphine ligands LR−azo and LS−azo. Owing to the cis‐trans photoisomerization of the azobenzene moiety, alkyne‐PdII/LR−azo and alkyne‐PdII/LS−azo exhibited different polymerization activities, helix‐sense selectivities, and enantioselectivities during the polymerization of isocyanide monomers under irradiation of different wavelength lights. Furthermore, the achiral isocyanide monomer A‐1 could be polymerized efficiently using alkyne‐PdII/LR−azo under dark condition in a living/controlled manner. Further, it generated single right‐handed helical poly‐A‐1m(LR−azo), confirmed by the circular dichroism spectra and atomic force microscopy images. However, the polymerization of A‐1 almost could not be initiated under 420 nm light in identical conditions of dark condition. Moreover, the photoswitchable catalyst alkyne‐PdII/LR−azo exhibited high enantioselectivity for the polymerization of the racemates of L‐1 and D‐1, respectively. D‐1 was polymerized preferentially under dark condition with a D‐1/L‐1 rate ratio of 70, yielding single right‐handed polyisocyanides. Additionally, reversible enantioselectivity was observed under 420 nm light using alkyne‐PdII/LR−azo, and the calculated polymerization rate ratio of L‐1/D‐1 was 57 because of the isomerization of the azobenzene moiety of the catalyst. Furthermore, alkyne‐PdII/LS−azo showed opposite enantioselectivity and helix‐sense selectivity during the polymerization of the racemates of L‐1 and D‐1.
Cobalt‐Catalyzed Electroreductive Alkylation of Unactivated Alkyl Chlorides with Conjugated Olefins
Authors: Al Zubaydi Samir , Onuigbo Immaculata O. , Truesdell Blaise L. , Sevov Christo S. 
Published: November 2023

AbstractReactions of unactivated alkyl chlorides under mild and sustainable conditions are rare compared to those of alkyl bromides or iodides. As a result, synthetic methods capable of modifying the vast chemical space of chloroalkane reagents, wastes, and materials are limited. We report the cobalt‐catalyzed reductive addition of unactivated alkyl chlorides to conjugated alkenes. Co‐catalyzed activation of alkyl chlorides is performed under electroreductive conditions, and the resulting reactions constitute formal alkyl‐alkyl bond formation. In addition to developing an operationally simple methodology, detailed mechanistic studies provide insights into the elementary steps of a proposed catalytic cycle. In particular, we propose a switch in the mechanism of C−Cl bond activation from nucleophilic substitution to halogen atom abstraction, which is critical for efficiently generating alkyl radicals. These mechanistic insights were leveraged in designing ligands that enable couplings of primary, secondary, and tertiary alkyl chlorides.
Mechanochemistry in Block Copolymers: New Scission Site due to Dynamic Phase Separation
Authors: Zhang Hang , Zoubi Alan Z. , Silberstein Meredith N. , Diesendruck Charles E. 
Published: November 2023

AbstractMechanochemistry can lead to the degradation of the properties of covalent macromolecules. In recent years, numerous functional materials have been developed based on block copolymers (BCPs), however, like homopolymers, their chains could undergo mechanochemical damage during processing, which could have crucial impact on their performance. To investigate the mechanochemical response of BCPs, multiple polymers comprising different ratios of butyl acrylate and methyl methacrylate were prepared with similar degree of polymerization and stressed in solution via ultrasonication. Interestingly, all BCPs, regardless of the amount of the methacrylate monomer, presented a mechanochemistry rate constant similar to that of the methacrylate homopolymer, while a random copolymer reacted like the acrylate homopolymer. Size‐exclusion chromatography showed that, in addition to the typical main peak shift towards higher retention times, a different daughter fragment was produced indicating a secondary selective scission site, situated around the covalent connection between the two blocks. Molecular dynamics modeling using acrylate and methacrylate oligomers were carried out and indicated that dynamic phase separation occurs even in a good solvent. Such non‐random conformations can explain the faster polymer mechanochemistry. Moreover, the dynamic model for end‐to‐end chain overstretching supports bond scission which is not necessarily chain‐centered.
A Microporous Hydrogen‐Bonded Organic Framework Based on Hydrogen‐Bonding Tetramers for Efficient Xe/Kr Separation
Authors: Huang Jiali , Li Yunbin , Zhang Hao , Yuan Zhen , Xiang Shengchang , Chen Banglin , Zhang Zhangjing 
Published: November 2023

AbstractHydrogen‐bonded organic frameworks (HOFs) have been emerging as a new type of very promising microporous materials for gas separation and purification, but few HOFs structures constructed through hydrogen‐bonding tetramers have been explored in this field. Herein, we report the first microporous HOF (termed as HOF‐FJU‐46) afforded by hydrogen‐bonding tetramers with 4‐fold interpenetrated diamond networks, which shows excellent chemical and thermal stability. What's more, activated HOF‐FJU‐46 exhibits the highest xenon (Xe) uptake of 2.51 mmol g−1 and xenon/krypton (Kr) selectivity of 19.9 at the ambient condition among the reported HOFs up to date. Dynamic breakthrough tests confirmed the excellent Xe/Kr separation of HOF‐FJU‐46a, showing high Kr productivity (110 mL g−1) and Xe uptake (1.29 mmol g−1), as well as good recyclability. The single crystal X‐ray diffraction and the molecular simulations revealed that the abundant accessible aromatic and pyrazole rings in the pore channels of HOF‐FJU‐46a can provide the multiple strong C−H⋅⋅⋅Xe interactions with Xe atoms.