bluuebunny/crossref_metadata_2025_split huggingface dataset:
Spheroidization: The Impact of Precursor Morphology on Solid‐State Lithiation Process for High‐Quality Ultrahigh‐Nickel Oxide Cathodes
Authors: Liang Wenbiao , Zhao Yin , Shi Liyi , Wang Zhuyi , Yuan Shuai 
Published: June 2024

AbstractLayered oxides with ultrahigh nickel content are considered promising high energy cathode materials. However, their cycle stability is constrained by a series of heterogeneous structural transformations during the complex solid‐state lithiation process. By in‐depth investigation into the solid‐state lithiation process of LiNi0.92Co0.04Mn0.04O2, it is found that the protruded parts on the surface of precursor particles tend to be surrounded by locally excessive LiOH, which promotes the formation of a rigid and dense
shell during the early stage of lithiation process. The shell will hinder the diffusion of lithium and topotactic lithiation within the particles, culminating in spatially heterogeneous intermediates that can impair the electrochemical properties of the cathode material. The spheroidization of the precursor can enhance uniformity in structural evolution during solid‐phase lithiation. Ultrahigh nickel cathodes derived from spherical precursors demonstrate high initial discharge specific capacity (234.2 mAh g−1, in the range of 2.7–4.3 V) and capacity retention (89.3 % after 200 cycles), significantly superior to the non‐spherical samples. This study not only sheds light on the intricate relationship between precursor shape and structural transformation but also introduces a novel strategy for enhancing cathode performance through precursor spheroidization.
Photocatalyzed Cascade Hydrogen Atom Transfers for Assembly of Multi‐Substituted α‐SCF3 and α‐SCF2H Cyclopentanones
Authors: Marie Nicolas , Ma Jun‐An , Tognetti Vincent , Cahard Dominique 
Published: June 2024

AbstractA photocatalyzed formal (3+2) cycloaddition has been developed to construct original polysubstituted α‐SCF3 cyclopentanones in a regio‐ and diastereoselective manner. This building block approach leverages trifluoromethylthio alkynes and branched/linear aldehydes, as readily available reaction partners, in consecutive hydrogen atom transfers and C−C bond formations. Difluoromethylthio alkynes are also compatible substrates. Furthermore, the potential for telescoped reaction starting from alcohols instead of aldehydes was demonstrated, as well as process automatization and scale‐up under continuous microflow conditions. This prompted density functional theory (DFT) calculations to support a radical‐mediated cascade process.
Reversible Modulation of Plasmonic Coupling of Gold Nanoparticles Confined within Swellable Polymer Colloidal Spheres
Authors: Ye Zuyang , Chen Chen , Cao Licheng , Cai Zepeng , Xu Christina , Kim Hye‐In , Giraldo Juan Pablo , Kanaras Antonios G. , Yin Yadong 
Published: June 2024

AbstractDynamic optical modulation in response to stimuli provides exciting opportunities for designing novel sensing, actuating, and authentication devices. Here, we demonstrate that the reversible swelling and deswelling of crosslinked polymer colloidal spheres in response to pH and temperature changes can be utilized to drive the assembly and disassembly of the embedded gold nanoparticles (AuNPs), inducing their plasmonic coupling and decoupling and, correspondingly, color changes. The multi‐responsive colloids are created by depositing a monolayer of AuNPs on the surface of resorcinol‐formaldehyde (RF) nanospheres, then overcoating them with an additional RF layer, followed by a seeded growth process to enlarge the AuNPs and reduce their interparticle separation to induce significant plasmonic coupling. This configuration facilitates dynamic modulation of plasmonic coupling through the reversible swelling/deswelling of the polymer spheres in response to pH and temperature changes. The rapid and repeatable transitions between coupled and decoupled plasmonic states of AuNPs enable reversible color switching when the polymer spheres are in colloidal form or embedded in hydrogel substrates. Furthermore, leveraging the photothermal effect and stimuli‐responsive plasmonic coupling of the embedded AuNPs enables the construction of hybrid hydrogel films featuring switchable anticounterfeiting patterns, showcasing the versatility and potential of this multi‐stimuli‐responsive plasmonic system.
Enhancing Ionic Selectivity and Osmotic Energy by Using an Ultrathin Zr‐MOF‐Based Heterogeneous Membrane with Trilayered Continuous Porous Structure
Authors: Yang Zhen‐Jie , Yeh Li‐Hsien , Peng Yu‐Hsiang , Chuang Yi‐Ping , Wu Kevin C.‐W. 
Published: June 2024

AbstractDesigning a nanofluidic membrane with high selectivity and fast ion transport property is the key towards high‐performance osmotic energy conversion. However, most of reported membranes can produce power density less than commercial benchmark (5 W/m2), due to the imbalance between ion selectivity and permeability. Here, we report a novel nanoarchitectured design of a heterogeneous membrane with an ultrathin and dense zirconium‐based UiO‐66‐NH2 metal–organic framework (MOF) layer and a highly aligned and interconnected branched alumina nanochannel membrane. The design leads to a continuous trilayered pore structure of large geometry gradient in the sequence from angstrom‐scale to nano‐scale to sub‐microscale, which enables the enhanced directional ion transport, and the angstrom‐sized (~6.6–7 Å) UiO‐66‐NH2 windows render the membrane with high ion selectivity. Consequently, the novel heterogeneous membrane can achieve a high‐performance power of ~8 W/m2 by mixing synthetic seawater and river water. The power density can be largely upgraded to an ultrahigh ~17.1 W/m2 along with ~48.5 % conversion efficiency at a 50‐fold KCl gradient. This work not only presents a new membrane design approach but also showcases the great potential of employing the zirconium‐based MOF channels as ion‐channel‐mimetic membranes for highly efficient blue energy harvesting.
Cobalt‐Catalyzed Photo‐Semipinacol Rearrangement of Unactivated Allylic Alcohols
Authors: Lindner Henry , Carreira Erick M. 
Published: June 2024

AbstractWe report a photochemical method for the semipinacol rearrangement of unactivated allylic alcohols. Aliphatic as well as aromatic groups participate as migrating groups, yielding a variety of α,α‐disubstituted ketones. The reaction proceeds under mild conditions and is compatible with ethers, esters, halides, nitriles, carbamates, and substituted arenes. The operationally simple and fully catalytic conditions prescribe 1 mol % benzothiazinoquinoxaline as organophotocatalyst, 0.5 mol % Co‐salen, and 10 mol % lutidinium triflate and, importantly, display reactivity complementary to procedures employing Brønsted acid. We showcase the utility of the protocol in late‐stage drug diversifications.
Unsymmetric Chiral Ligands for Large Metallo‐Macrocycles: Selectivity of Orientational Self‐Sorting
Authors: Jurček Ondřej , Chattopadhyay Subhasis , Kalenius Elina , Linnanto Juha M. , Kiesilä Anniina , Jurček Pia , Radiměřský Petr , Marek Radek 
Published: June 2024

AbstractNature uses various chiral and unsymmetric building blocks to form substantial and complex supramolecular assemblies. In contrast, the majority of organic ligands used in metallosupramolecular chemistry are symmetric and achiral. Here we extend the group of unsymmetric chiral bile acids used as a scaffold for organic bispyridyl ligands by employing chenodeoxycholic acid (CDCA), an epimer of the previously used ursodeoxycholic acid (UDCA). The epimerism, flexibility, and bulkiness of the ligands leads to large structural differences in coordination products upon reaction with Pd(NO3)2. The UDCA‐bispyridyl ligand self‐assembles quantitatively into a single crown‐like Pd3L6 complex, whereas the CDCA ligand provides a mixture of coordination complexes of general formula PdnL2n, i.e., Pd2L4, Pd3L6, Pd4L8, Pd5L10, and even Pd6L12 containing an impressive 120 chiral centers. The coordination products were studied by a combination of analytical methods, with ion‐mobility mass spectrometry (IM‐MS) providing valuable details on their structure and allowed an effective separation of m/z 1461 to individual signals according to the arrival time distribution, thereby revealing four different ions of [Pd3L6(NO3)3]3+, [Pd4L8(NO3)4]4+, [Pd5L10(NO3)5]5+, and [Pd6L12(NO3)6]6+. The structures of all the complexes were modelled using DFT calculations. Finally, the challenges and conclusions in determining the specific structural identity of these unsymmetric species are discussed.
Reducing risk: navigating emotional triangles in clinical work with youth suicidality and self‐harm
Authors: Wright Jo , Milligan Robyn , Varcoe Michelle 
Published: June 2024

AbstractIn clinical work with families in which a young person is at real and significant risk of self‐harm or even death by suicide, predictable emotional triangles both within the family and within the treating system intensify. As understandable fear and worry in parents and clinicians rises in response to potential risk, these emotionally driven relational processes become even more rigid. This typically results in a reduction in cognitive and behavioural flexibility, which can potentially and unwittingly increase the risk of self‐harm by suicide. This article outlines some basic principles pertaining to the notion of emotional triangles, a central concept in Bowen family systems theory; its relevance for clinicians working with suicidal youth and their families; and its application to the context of a community child and youth mental health service. Practical application of theory to clinical work is demonstrated through clinical vignettes that describe the work of two clinicians and their clinical supervisor. The authors reflect on their understanding of the development of emotional triangles in the vignettes presented alongside their efforts to navigate these triangles through the regulation of their own anxiety and more objective thinking.
Reactivity, processability, and thermal stability of tetrafunctional glycidyl ether cyclic siloxane epoxy hybrid networks
Authors: Gan Houlei , Seraji Seyed Mohsen , Khan Masihullah Jabarulla , Zhang Juan , Swan Samuel R. , Senanayake Rusheni Bhagya , Varley Russell J. 
Published: June 2024

AbstractA low viscosity tetra‐functional cyclosiloxane epoxy resins (TGTS) is synthesized via a one‐step hydrosilylation reaction and cured separately with four different aromatic diamines to explore the reaction kinetics, network development, and thermal resistance. The hardeners used are 1,3‐phenylenediamine (PDA), diethyl toluene diamine (DETDA), 4,4‐diaminodiphenylmethane (DDM), and 1,3‐bis(4‐aminophenoxy) benzene, because of their availability and aromaticity. During cure with TGTS they all display autocatalytic behavior, but when compared to a traditional organic epoxy resin, diglycidyl ether of bisphenol A (DGEBA) cured with DDM however, the rate constants are about 3 times slower and less exothermic. The DETDA hardener in particular exhibits significantly slower rates of cure when compared to the other amines, being about an order of magnitude slower compared to the PDA curative. This is attributed to higher steric hindrance, compounded by reduced miscibility. The TGTS‐DDM carbon fiber composite displays the most thermal resistance after extended exposure to 220°C, producing the least mass loss and after combustion of about 12% compared to 20% for the DGEBA cured with DDM. The results presented here, illustrate that a tetrafunctional cyclic siloxane epoxy resin, can exhibit excellent processability, evidenced by very low viscosities and long gelation times, whilst also displaying excellent thermal resistance, whether at elevated temperature, or during combustion.
Multi‐responsive co‐assembled polyurethane nanomicelles as anticancer drug delivery carriers
Authors: Liu Zhaoxia , Zhao Lili , Tao Wangwang , Chen Rui , Zhou Yu , Chen Hongxiang , Yan Hongye , Liao Xinghua 
Published: June 2024

AbstractIn order to obtain a kind of anticancer drug delivery carriers with good stability in blood circulation, high cellular uptake, and controlled drug release ability, folate‐modified polyurethane with disulfide bonds and amino groups (FPUSN) and polyurethane with carboxyl groups (PUC) were respectively synthesized. FPUSN and PUC could co‐assemble in water to form nanomicelles (FPUSN/PUC) via electrostatic interaction. When the mass ratio of FPUSN to PUC was 12, FPUSN/PUC‐12 micelles had obvious negative‐to‐positive charge‐reversal property with decreasing pH from 7.4 to 5.0. Doxorubicin‐loaded micelles (FPUSN/PUC‐12@DOX) with negative charges showed excellent stability under simulated normal physiological condition. However, the charge‐reversal happened at pH 6.5 and positive charges increased with the pH decrease. When the glutathione concentration was 10 mM, the structure of FPUSN/PUC‐12@DOX micelles was broken. So FPUSN/PUC‐12@DOX micelles exhibited significant acid/reduction‐sensitive drug release properties and then DOX could be rapidly released in simulated tumor intracellular environment. Cellular experimental results demonstrated that FPUSN/PUC‐12 micelles could enhance cellular uptake under acid condition and FPUSN/PUC‐12@DOX micelles had better anti‐proliferation effect against HGC‐27 cells at pH 6.5 than that at pH 7.4 owing to multi‐responsive synergistic effects. Therefore, FPUSN/PUC micelles will have great application potential as drug delivery carriers for enhancing anticancer efficacy.
Nachhaltiger Betrieb der Tunnelentwässerung ohne Schachtabdeckungen in der Fahrbahn
Authors: Bornschier Christian , Klehm Torsten , Ranft Andreas 
Published: June 2024

AbstractEine gut geplante Entwässerungsanlage im Bereich des Straßenkörpers und der darin integrierten Ingenieurbauwerke trägt maßgeblich zur Verkehrssicherheit bei. Gleichzeitig reduziert eine geschickte Planung in Verbindung mit geeigneten Materialien und Konstruktionen langfristig die Unterhaltungskosten und sorgt so für einen reibungslosen Betrieb der Anlage. Die Wartungsfreundlichkeit des Systems hat einen großen Anteil an der Minimierung von Sperrzeiten für Reinigungs‐ und Instandsetzungsarbeiten. Gerade bei Tunnelbauwerken sorgen u. a. die Entwässerungssysteme regelmäßig für Sperrungen aufgrund von Wartung und Instandsetzung. Besonders im Bereich der permanent überfahrenen Kontrollschächte kommt es immer wieder zu Schäden, deren Behebung mitunter zu langen Sperrzeiten der Verkehrswege führt. Mit dem Einsatz eines modifizierten Tauchwandschachts am Fahrbahnrand – ohne Schachtdeckel in der Fahrbahn – sollen der Betrieb, die Unterhaltung der Entwässerungsleitung und die daraus resultierenden Kosten reduziert werden. In vorliegendem Beitrag werden der modifizierte Tauchwandschacht und dessen Vorteile für den Betrieb von Tunnelbauwerken vorgestellt.
Trans‐rectovesical pouch urethral‐sparing robotic‐assisted simple prostatectomy: A case series
Authors: Chen Xinnan , Zhao Kangkang , Wang Hao , Zhang Chengwei , Du Lin , Wang Wendi , Chen Tianyi , Qin Haixiang , Qiu Xuefeng , Guo Hongqian , Zhang Gutian 
Published: June 2024

AbstractObjectiveTo detail a novel technique of robotic‐assisted simple prostatectomy that makes handling the gland protruding into the bladder neck easier and can preserve the urethra and retain ejaculation function as much as possible.Patients and methodsThis is a prospective case series. Clinical data of 17 male patients who had large volume (>80 mL) benign prostatic hyperplasia (BPH) were enrolled to undergo trans‐rectovesical pouch urethral‐sparing robotic‐assisted simple prostatectomy (usRASP). We adopted the approach through the space between the bladder neck and seminal vesicle to perform a usRASP that can avoid the detrusor skirt and fibrous matrix area of the retropubic prostate. Between the transitional zone and the peripheral zone of the large prostate, the hyperplastic prostatic gland tissue can be enucleated under direct vision while preserving the prostatic urethra and retaining the ejaculatory duct and bladder neck intact. All preoperative, perioperative and postoperative clinical data were collected, and descriptive analysis was performed.ResultsThe median intravesical prostatic protrusion was 19.3 mm (8.5–32.2). The median operative time was 100 min (75–140), and the median estimated blood loss was 100 mL (10–500). The median time to catheter removal was 7 days (5–7), with a median postoperative hospital stay of 2 days (2–4). After at least 6‐month follow‐up, the median maximum urine flow rate and postvoid residual volume were 40.1 mL/s (12.7–52.4) and 15 mL (5–23), respectively; the median International Prostate Symptom Score and Quality of Life score were 0 (0–6.3) and 1 (0–3), respectively; and the median total prostate‐specific antigen was 0.84 ng/mL (0.15–1.01). All patients successfully underwent usRASP. Fifty‐eight percent of patients with normal ejaculation function before surgery can still retain normal ejaculation function.ConclusionWe described a new approach to performing usRASP. This new method remarkably improved the voiding function, maintained antegrade ejaculation and did not increase the post‐operative complications.
Enhancing the durability of anion exchange membrane water electrolysis cells via interfacial membrane–ionomer crosslinking
Authors: Lee Yerim , Lee Wooseok , Kim Tae‐Hyun 
Published: June 2024

AbstractResearch into enhancing the performance and durability of anion exchange membrane (AEM)‐based water electrolysis (AEMWE) cells has primarily aimed to facilitate commercialization efforts and improve the chemical stability of AEMs, with anion exchange ionomers (AEIs) playing an increasingly important role. This study aimed to reduce ionomer swelling and enhance AEM–catalyst adhesion via AEM–ionomer crosslinking within a membrane electrode assembly (MEA), using allyl‐ and quaternary ammonium‐functionalized poly(phenylene oxide) (PPO), allyl‐m‐PPO, as both the AEM and AEI. Bis(aryl azide) was added as a crosslinker to an ionomer solution to generate the MEA, which was heated to induce allyl–azide crosslinks at the membrane–ionomer interface. Peel test indicated an increased adhesion at both electrodes for the crosslinked x‐allyl‐0.05‐PPO (5 mol% allyl content relative to the total ion‐conducting head group content). Further, x‐allyl‐0.05‐PPO exhibited a smaller voltage increase due to crosslinking compared to TA‐PPO, signifying a notable improvement in durability.
Greening by digitization? Exploring the effect of enterprise digital transformation on greenwashing
Authors: Wang Shanyong , Lai Yancheng , Zhang Shuainan 
Published: June 2024

AbstractGreenwashing has become an important strategy for enterprises to cope with the intense pressure on environmental sustainability and to gain environmental legitimacy. Digital transformation has an important impact on enterprise decision‐making and environmental management. Based on panel data of Chinese A‐share listed enterprises from 2011 to 2021, we empirically examine the relationship between digital transformation and greenwashing using a fixed‐effects model. The results show that enterprise digital transformation can significantly inhibit greenwashing behavior. Second, the impact of enterprise digital transformation on greenwashing exhibits heterogeneous effects at the regional, industry, and firm levels. Furthermore, enterprise digital transformation suppresses greenwashing by alleviating financing constraints, improving information transparency, and enhancing internal control. In addition, we also find that there is an effective boundary to the impact of digital transformation on greenwashing. Specifically, digital transformation exerts a mitigating impact on enterprise greenwashing when the digital transformation level is lower than 10.2163 or higher than 15.7763. Our findings provide references for managers and policy makers to understand digital transformation and its impact on greenwashing.
Explainable machine learning predicts survival of retroperitoneal liposarcoma: A study based on theSEERdatabase and external validation in China
Authors: Wang Maoyu , Li Zhizhou , Zeng Shuxiong , Wang Ziwei , Ying Yidie , He Wei , Zhang Zhensheng , Wang Huiqing , Xu Chuanliang 
Published: June 2024

AbstractObjectiveWe have developed explainable machine learning models to predict the overall survival (OS) of retroperitoneal liposarcoma (RLPS) patients. This approach aims to enhance the explainability and transparency of our modeling results.MethodsWe collected clinicopathological information of RLPS patients from The Surveillance, Epidemiology, and End Results (SEER) database and allocated them into training and validation sets with a 7:3 ratio. Simultaneously, we obtained an external validation cohort from The First Affiliated Hospital of Naval Medical University (Shanghai, China). We performed LASSO regression and multivariate Cox proportional hazards analysis to identify relevant risk factors, which were then combined to develop six machine learning (ML) models: Cox proportional hazards model (Coxph), random survival forest (RSF), ranger, gradient boosting with component‐wise linear models (GBM), decision trees, and boosting trees. The predictive performance of these ML models was evaluated using the concordance index (C‐index), the integrated cumulative/dynamic area under the curve (AUC), and the integrated Brier score, as well as the Cox–Snell residual plot. We also used time‐dependent variable importance, analysis of partial dependence survival plots, and the generation of aggregated survival SHapley Additive exPlanations (SurvSHAP) plots to provide a global explanation of the optimal model. Additionally, SurvSHAP (t) and survival local interpretable model‐agnostic explanations (SurvLIME) plots were used to provide a local explanation of the optimal model.ResultsThe final ML models are consisted of six factors: patient's age, gender, marital status, surgical history, as well as tumor's histopathological classification, histological grade, and SEER stage. Our prognostic model exhibits significant discriminative ability, particularly with the ranger model performing optimally. In the training set, validation set, and external validation set, the AUC for 1, 3, and 5 year OS are all above 0.83, and the integrated Brier scores are consistently below 0.15. The explainability analysis of the ranger model also indicates that histological grade, histopathological classification, and age are the most influential factors in predicting OS.ConclusionsThe ranger ML prognostic model exhibits optimal performance and can be utilized to predict the OS of RLPS patients, offering valuable and crucial references for clinical physicians to make informed decisions in advance.