bluuebunny/crossref_metadata_2025_split huggingface dataset:
Early Addition of Selexipag to Double Therapy for Pulmonary Arterial Hypertension
Authors: Burger Charles D. , Tang Wenze , Tsang Yuen , Panjabi Sumeet 
Published: September 2024

ImportanceA subgroup analysis of a randomized clinical trial established the efficacy of selexipag plus background therapy (monotherapy or double oral therapy [DOT]) vs placebo plus background therapy and found that the addition of selexipag within 6 months had an added benefit. However, the timing of selexipag addition to DOT and the incremental benefit in clinical practice is not well studied.ObjectiveTo compare triple oral therapy (TOT) consisting of selexipag, endothelin receptor antagonist (ERA), and phosphodiesterase type 5 inhibitor (PDE5i) vs DOT consisting of ERA and PDE5i.Design, Setting, and ParticipantsThis comparative effectiveness study was conducted using data from the US Komodo claims database to emulate a randomized trial. Patients aged 18 years or older with pulmonary arterial hypertension (PAH) treated with ERA plus PDE5i with records from July 2015 through June 2022 were duplicated to TOT and DOT and artificially censored when observed treatment deviated from assigned treatment. Hypothetical randomization was emulated using inverse probability of treatment weighting, and the study accounted for censoring-induced selection bias using inverse probability of censoring weighting. A pooled logistic model estimated the per-protocol difference between treatment groups. Data were analyzed from November 2022 through July 2023.InterventionsTOT (addition of selexipag within 3, 6, and 12 months of initiating DOT) vs DOT.Main Outcomes and MeasuresAdjusted risk of all-cause hospitalization, PAH-related hospitalization, and PAH-related disease progression over a 2-year follow-up.ResultsA total of 2966 patients with PAH (mean [SD] age, 54.3 [14.0] years; 2125 female [71.6%]) met eligibility criteria. Adding selexipag within 6 months of ongoing DOT was associated with a reduction in risk for all-cause hospitalization (adjusted hazard ratio [aHR], 0.82; 95% CI, 0.72-0.94), PAH-related hospitalization (aHR, 0.81; 95% CI, 0.70-0.95), and PAH-related progression (aHR, 0.82; 95% CI, 0.70-0.95) vs DOT alone. There were no associations if selexipag was initiated within 12 months for all-cause hospitalization, PAH-related hospitalization, or PAH-related disease progression. The association remained with a greater decrease in risk for disease progression vs DOT for selexipag initiation within 3 months (aHR, 0.74; 95% CI, 0.61-0.90).Conclusions and RelevanceThis study found that early selexipag addition to ERA plus PDE5i was associated with a reduction in risk of hospitalization and disease progression. These findings suggest that delays in selexipag initiation likely contribute to suboptimal patient and health system outcomes.
Gender Representation of Health Care Professionals in Large Language Model–Generated Stories
Authors: Menz Bradley D. , Kuderer Nicole M. , Chin-Yee Benjamin , Logan Jessica M. , Rowland Andrew , Sorich Michael J. , Hopkins Ashley M. 
Published: September 2024

ImportanceWith the growing use of large language models (LLMs) in education and health care settings, it is important to ensure that the information they generate is diverse and equitable, to avoid reinforcing or creating stereotypes that may influence the aspirations of upcoming generations.ObjectiveTo evaluate the gender representation of LLM-generated stories involving medical doctors, surgeons, and nurses and to investigate the association of varying personality and professional seniority descriptors with the gender proportions for these professions.Design, Setting, and ParticipantsThis is a cross-sectional simulation study of publicly accessible LLMs, accessed from December 2023 to January 2024. GPT-3.5-turbo and GPT-4 (OpenAI), Gemini-pro (Google), and Llama-2-70B-chat (Meta) were prompted to generate 500 stories featuring medical doctors, surgeons, and nurses for a total 6000 stories. A further 43 200 prompts were submitted to the LLMs containing varying descriptors of personality (agreeableness, neuroticism, extraversion, conscientiousness, and openness) and professional seniority.Main Outcomes and MeasuresThe primary outcome was the gender proportion (she/her vs he/him) within stories generated by LLMs about medical doctors, surgeons, and nurses, through analyzing the pronouns contained within the stories using χ2 analyses. The pronoun proportions for each health care profession were compared with US Census data by descriptive statistics and χ2 tests.ResultsIn the initial 6000 prompts submitted to the LLMs, 98% of nurses were referred to by she/her pronouns. The representation of she/her for medical doctors ranged from 50% to 84%, and that for surgeons ranged from 36% to 80%. In the 43 200 additional prompts containing personality and seniority descriptors, stories of medical doctors and surgeons with higher agreeableness, openness, and conscientiousness, as well as lower neuroticism, resulted in higher she/her (reduced he/him) representation. For several LLMs, stories focusing on senior medical doctors and surgeons were less likely to be she/her than stories focusing on junior medical doctors and surgeons.Conclusions and RelevanceThis cross-sectional study highlights the need for LLM developers to update their tools for equitable and diverse gender representation in essential health care roles, including medical doctors, surgeons, and nurses. As LLMs become increasingly adopted throughout health care and education, continuous monitoring of these tools is needed to ensure that they reflect a diverse workforce, capable of serving society’s needs effectively.
Influence of Ni‐Coating Thickness on Interface Microstructure and Mechanical Properties of Mg/Ti Bimetal via Compound Casting
Authors: Wu Yuanbing , Zhao Jianhua , Wei Chao , Gu Cheng 
Published: September 2024

In this article, the influence of Nickel (Ni)coating thickness on the interfacial microstructure and mechanical properties of AZ91D/Ti–6Al–4 V bimetal fabricated by compound casting is investigated. In the results, it is shown that the Ni coating and its thickness have a significant effect on the interfacial phase compositions and mechanical properties of AZ91D/Ti–6Al–4 V bimetal. At a Ni‐coating thickness of 6.5–27.3 μm, it transforms into α‐Mg + Mg2Ni eutectic structures + blocky τ‐Ni2Mg3Al ternary compounds at the interface zone. When the Ni‐coating thickness increases to 36.1 μm, part of the Ni coating remains, and the interface layer forms, comprising the Ni solid solution layer, Mg2Ni layer, τ‐Ni2Mg3Al ternary compounds, and α‐Mg + τ‐Ni2Mg3Al particles from Ti–6Al–4 V to AZ91D side in sequence. The microhardness of the interface zone is lower than that of the Ti–6Al–4 V but higher than AZ91D. The bimetal shear strength reaches a maximum value of 87.6 MPa at a Ni‐coating thickness of 19.7 μm enhanced by 78.5% in comparison with that of the bimetal without Ni coating. The results are helpful to further enrich the interface control method of compound casting of Ti/Mg bimetal and determine the ideal interlayer thickness for maximizing interface strength.
SnAgCu Solder Joint Microstructure Evolution During Thermal Aging: Influence of Flux
Authors: Veselý Petr , Králová Iva , Pilnaj Dominik , Plaček Martin , Dušek Karel 
Published: September 2024

An intermetallic layer (IML) between the solder alloy and the soldered surface affects the mechanical and electrical performance of the resulting joints. Numerous studies have explored the possibilities of influencing the IML to achieve more reliable interconnections. However, the type and composition of the used flux, crucial for the proper creation of solder joints, is rarely included as a possible influencing factor. In this article, a comprehensive study on the interfacial microstructure evolution of lead‐free SnAgCu solder joints, accounting for the flux type and the temperature of the preheating phase of reflow soldering, where the flux contained in the solder paste becomes active, is presented. In the results, it is shown that the IML of as‐reflowed and thermally aged solder joints depends significantly on the flux. The IML activation energy is 57% higher for rosin‐based low‐activity (ROL)0 flux compared to ROL1 flux. The ROL0 flux, containing fewer active components, also outperforms the ROL1 flux in both the mechanical and electrical properties of the joints. Furthermore, the temperature profiles also show slight differences in measured properties, with the fluxes responding differently to changes in preheating temperature. In the presented results, importance of the used flux on solder joint microstructure is demonstrated.
Photo Electrocatalytic Water Splitting Using Sn Doped In2S3 Homologous Series Synthesized in Oxygen Deficient Flame
Authors: Pokhrel Suman , Stahl Jakob , Wang Lizhuo , Tang Rui , Sun Haoyue , Schalk Malte , Schowalter Marco , Rosenauer Andreas , Huang Jun , Kiefer Johannes , Birkenstock Johannes , Mädler Lutz 
Published: September 2024

AbstractThe innovative development of reactive‐spray systems for gas‐phase production of metal sulfides are potential materials for next‐generation technologies. These flame‐synthesized sulfides (doped, functionalized, and heterogeneously mixed derivatives) hold significant potential as photocatalysts for water splitting. The knowledge acquired from nonaqueous precursor‐solvent and high‐temperature aerosol chemistries, optimal process parameters are established to generate In2‐(4/3)xSnxS3, solid‐solutions. The thermally driven reducing gas‐phase reactions are controlled through fuel/oxygen ratio. Particles characterizations (X‐ray diffraction, transmission electron microscopy (TEM) and imaging) revealed structural stability and crystallinity. The In2‐(4/3)xSnxS3, at higher Sn doping had enhanced photoexcitation. Donor‐acceptor levels within the material facilitated electron‐hole pair trapping, crucial for redox reactions. With suitable band gap energies for water oxidation (1.9‐1.1 eV) closely matched flat band potentials (4.38‐4.67 eV) for redox reactions. The powder characterization showed 8% In2O3 in InSn0.75S3 after photocatalysis due to S‐degradation in the initial light “on/off cycles”. The pioneering process of employing oxygen‐deficient reducing flame enabled a series of photo‐catalytically active metal sulfide nanoparticles with work function energies in the range of 5.19‐5.37 eV. This synthesis strategy holds the potential for impactful advancements in both industry and R&D, addressing the urgent need for new materials capable of inducing water oxidation under visible light.
Ultrasmall Sulfur‐Dots‐Mediated Facile Photopolymerization for the Production of Smart Injectable Ink for 3D Printing Applications
Authors: Singh Nishikanta , Sinha Priyank , Sahu Bhanendra , Mandal Srayee , Bhattacharyya Santanu , Banerjee Sanjib 
Published: September 2024

AbstractSulfur dots (S‐dots) eliminate the need of expensive and toxic conventional photocatalysts or transition metal in photoinduced reversible deactivation radical polymerization (photoRDRP). Herein, non‐metallic S‐dots mediated photoRDRP of N,N‐dimethyl acrylamide (DMA) are developed for the first time. This technique allows for the precise synthesis of narrow‐dispersed poly(N,N‐dimethyl acrylamide) (PDMA) and double hydrophilic poly(N, N‐dimethyl acrylamide)‐block‐poly(2‐hydroxyethyl acrylamide) (PDMA‐b‐PHEAA) diblock copolymer suitable for contaminant removal from water. Also, its subsequent modification into a poly(N,N‐dimethyl acrylamide)‐block‐poly(N‐(2‐((4‐vinylbenzyl)oxy)ethyl)acrylamide) (PDMA‐b‐PVBEAA) diblock copolymer gives ultra‐fast gelation and production of writable ink‐gel, which is exceptionally well‐suited for 3D printing applications, enabling the creation of precise and defined shapes. This innovative material serves as an intriguing scaffold for tissue engineering and other biomaterial applications, especially in areas that demand rapid and customizable manufacturing solutions.
Sensor‐Embedded Muscle for Closed‐Loop Controllable Actuation in Proprioceptive Biohybrid Robots
Authors: Filippi Miriam , Balciunaite Aiste , Georgopoulou Antonia , Paniagua Pablo , Drescher Felix , Nie Minghao , Takeuchi Shoji , Clemens Frank , Katzschmann Robert K. 
Published: September 2024

Biohybrid robots are soft robots that exploit unique characteristics of biological cells and tissues for motion generation. Skeletal muscle tissue‐based bioactuators respond to externally applied stimuli, such as electrical fields. However, current bioactuation systems rely on open‐loop control strategies that lack knowledge of the actuator's state. The regulation of output force and position of biohybrid robots requires self‐sensing control systems that combine bioactuators with sensors and control paradigms. Herein, a soft, fiber‐shaped mechanical sensor based on a piezoresistive composite is proposed that efficiently integrates with engineered skeletal muscle tissue and senses its contracting states in a cell culture environment in the presence of applied electrical fields. After testing the sensor's insulation and biocompatibility, its sensitivity for typical strains (<1%) is characterized, and its ability is proven to detect motions from contractile skeletal muscle tissue constructs. Finally, it is shown that the sensor response can feed an autonomous control system, thus demonstrating the first proprioceptive biohybrid robot that senses and responds to its contraction state. In addition to inspiring implantable systems, biomedical models, and other bioelectronic devices, the proposed technology will confer biohybrids with decisional autonomy, thus driving the paradigm shift between bioactuators and intelligent biohybrid robots.
Intermolekulare 1,2‐Aminoborierung von Alkinen und die Kritische Rolle Elektronenreicher Alkine
Authors: Dotzauer Simon , Jayaraman Arumugam , Reinhart David , Braunschweig Holger 
Published: September 2024

AbstractWährend die intramolekulare 1,2‐Aminoborierung von Alkinen durch Aminoborane selten ist und stets einen Katalysator erfordert, ist die intermolekulare Aminoborierung von Alkinen noch gänzlich unerforscht. Dank Untersuchungen der elektronischen Faktoren, die zur Aktivierung der B−N‐σ‐Bindung von Aminoboranen durch Alkine beitragen, legen wir in dieser Arbeit die erste intermolekulare 1,2‐Aminoborierung von Alkinen dar. Diese Reaktionen, in denen eine Reihe von (Amino)dihalogenboranen und Aminoborsäureestern verwendet wird, laufen unter milden Bedingungen und ohne Katalysatoren ab, was zu syn‐Additionsprodukten führt, die zwei entscheidende Funktionalitäten aufweisen, nämlich Amino‐ und Borylgruppen. Während besonders elektronenreiche Alkine (Z)‐2‐Borylethenamine liefern, führen andere, weniger aktivierte bzw. elektronenärmere Alkine aufgrund endergoner Reaktionen nicht zu den entsprechenden Aminoborierungsprodukten.
Catalytic Edges in One‐Dimensional Covalent Organic Frameworks for the Oxygen Reduction Reaction
Authors: Chang Yumeng , Lin Chao , Wang Haifeng , Wu Xiaotong , Zou Luyao , Shi Jixin , Xiao Qi , Xu Qing , Li Xiaopeng , Luo Wei 
Published: September 2024

AbstractMetal‐free covalent organic frameworks (COFs) are employed in oxygen reduction reactions (ORR) because of their diverse structural units and controllable catalytic sites, and the edge sites have high catalytic activity than the basal sites. However, it is still challenge to modulate the edge sites in COFs, because the extended frameworks in two‐ or three‐dimensional topologies resulted in limited edge parts. In this study, we have demonstrated the edge site modulation engineering based on one dimensional (1D) COFs to catalyze the ORR, which featured distinct edge groups‐carbonyl, diaminopyrazine, phenylimidazole, and benzaldehyde imidazole units. The synthesized COFs have same ordered frameworks, similar pore structure, but had different electronic states of the carbons along the edge sites, which results in tailored catalytic properties. Notably, the COF functionalized with a phenylimidazole edge group exhibited superior catalytic performance compared to the other synthesized COFs. And the theoretical calculation further revealed the different edge sites had tunable binding ability of the intermediates OOH*, which contributed modulated activity. Our findings introduce a novel way for designing COFs optimized for ORR applications through molecular level control of edge sites.
Bidentate Coordination Enables Anions‐Regulated Solvation Structure for Advanced Aqueous Zinc Metal Batteries
Authors: Wang Dongdong , Li Rui , Dong Jingjing , Bai Zhongchao , Wang Nana , Dou Shi Xue , Yang Jian 
Published: September 2024

AbstractRechargeable aqueous Zn metal batteries (AZMBs) are attractive for stationary energy storage due to their low cost and high safety. However, their practical application is hindered by the excessive use of zinc anodes and poor high‐temperature performance, caused by severe side reactions and dendritic growth issues. Here, an electrolyte design strategy is reported based on bidentate coordination of Zn2+ and solvent to tailor the solvation structure. The triethylene glycol (TEG) co‐solvent with two‐oxygen coordination sites is demonstrated to facilitate the formation of an anions‐involved solvation shell, greatly reducing the activity of coordinated H2O molecules. The sequential reduction of OTF− anions and TEG leads to the formation of an organic–inorganic bilayer SEI (hydrophobic organic layer and high ion conductivity inorganic layer), protecting Zn anodes from side reactions and dendrite growth, thus ensuring an unprecedented Zn reversibility (99.95 % over 5000 cycles at 0.5 mA cm−2). More importantly, the full cells of Zn||V2O5 exhibit a record‐high cumulative capacity (2552 mAh cm−2) under a lean electrolyte condition (E/C ratio=15 μl mAh−1), a limited Zn supply (N/P ratio=1.9) and a high areal capacity (3.0 mAh cm−2).
Correspondence on “Visible‐Light‐Switchable Chalcone‐Flavylium Photochromic Systems in Aqueous Media”
Authors: Basílio Nuno , Parola A. Jorge , Pina Fernando 
Published: September 2024

AbstractIn a recent Communication in this journal, Bandyopadhyay and co‐workers proposed a rational design of chalcone photoswitches that are claimed to convert into the respective flavylium cations upon irradiation with blue, green, and red light in aqueous media. Here we argue that the reported improvements on the optical/photochemical properties of the new chalcone photoswitches are not substantiated and that the proposed design and data interpretation rely on assumptions that have yet to be validated. We also identify a series of control experiments that can be performed to verify the hypotheses and better support the conclusions presented by the authors.
Nanohoops Favour Light‐Induced Energy Transfer over Charge Separation in Porphyrin/[10]CPP/Fullerene Rotaxanes
Authors: Schwer Fabian , Zank Simon , Freiberger Markus , Steudel Fabian M. , Geue Niklas , Ye Lei , Barran Perdita E. , Drewello Thomas , Guldi Dirk M. , von Delius Max 
Published: September 2024

Abstract[2]Rotaxanes offer unique opportunities for studying and modulating charge separation and energy transfer, because the mechanical bond allows the robust, yet spatially dynamic tethering of photoactive groups. In this work, we synthesized [2]rotaxane triads comprising a central (aza)[10]CPP⊃C60 bis‐adduct complex and two zinc porphyrin stoppers to address how the movable nanohoop affects light‐induced charge separation and energy transfer between the rotaxane subcomponents. We found that neither the parent nanohoop [10]CPP nor its electron‐deficient analogue aza[10]CPP actively participate in charge separation. In contrast, the nanohoops completely prevented through‐space charge separation. This result is likely due to supramolecular “shielding”, because charge separation was observed in the thread that acted as reference dyad. On the other hand, the suppression of electron transfer allowed the observation of energy transfer from the porphyrin triplet to the fullerene triplet state with a lifetime of ca. 25 μs. The presence of the interlocked nanohoops therefore leads to a dramatic switch between charge separation and energy transfer. We suggest that our results explain observations made by others in photovoltaic devices comprising nanohoops and may pave the way toward strategic uses of mechanically interlocked architectures in devices that feature (triplet) energy transfer.
Single‐Atom Catalysts with p‐Block Metals Surpass Transition‐Metal Counterparts in the Photocatalytic H2O2 Production
Authors: Lu Haijiao , Yin Hanqing , Harmer Jeffrey , Xiao Mu , You Jiakang , Chen Peng , Lin Tongen , Du Aijun , Wang Zhiliang , Wang Lianzhou 
Published: September 2024

AbstractGrowing interest in p‐block metal single‐atom catalysts (PM‐SACs) is driven by their low toxicity, economic viability, and transition metal‐like catalytic properties. However, selection criteria for p‐block single‐atom species and catalytic mechanisms of PM‐SACs remain unclear. This study explores the catalytic abilities of PM‐SACs and their transition metal counterparts (TM‐SACs) based on polymetric carbon nitride (PCN) for photocatalytic hydrogen peroxide (H2O2) production. Using thermodynamic barriers as a key descriptor, it was found that PM‐SACs can surpass TM‐SACs in H2O2 production due to a lower energy barrier for *OOH intermediate formation resulting from optimized p‐p hybridization. Specifically, Sb‐SAC based on PCN shows the highest apparent quantum yield of 35.3 % at 400 nm. This study offers a rationale for the utilization of p‐block SACs in the context of sustainable chemical synthesis.
Harnessing 4f Electron Itinerancy for Integrated Dual‐Band Redox Systems Boosts Lithium‐Oxygen Batteries Electrocatalysis
Authors: Huang Mengyao , Song Lina , Wang Nan , Fu Yaning , Ren Rongchang , Li Zhongjun , Lu Youcai , Xu Jijing , Liu Qingchao 
Published: September 2024

AbstractIn‐depth comprehension and manipulation of band occupation at metal centers are crucial for facilitating effective adsorption and electron transfer in lithium‐oxygen battery (LOB) reactions. Rare earth elements play a unique role in band hybridization due to their deep orbitals and strong localization of 4 f electrons. Herein, we anchor single Ce atoms onto CoO, constructing a highly active and stable catalyst with d‐f a dual‐band redox center. It is discovered that the itinerant behavior of 4 f electrons introduces an enhanced spin‐orbit coupling effect, which facilitates ideal σ/π bonding and flexible adsorption between the Ce/Co active sites and *O. Simultaneously, the injection of localized Ce 4 f electrons strengthens the orbital bonding capacity of Co−O, effectively inhibits the dissolution of Co sites and improves the structural stability of the cathode material. Bracingly, the Ce1/CoO‐based LOB exhibits an ultra‐low charge–discharge polarization (0.46 V) and stable cyclic performance (1088 hours). This work breaks through the traditional limitations in catalyst activity and stability, providing new strategies and theoretical insights for developing high‐performance LOBs powered by rare‐earth elements.