bluuebunny/crossref_metadata_2025_split huggingface dataset:
Bidirectional Associations of Depressive Symptoms and Cognitive Function Over Time
Authors: Yin Jiamin , John Amber , Cadar Dorina 
Published: June 2024

ImportanceCognitive decline and depressive symptoms often co-occur among older adults, and they share several mechanisms. Despite the fact that cognitive dysfunction has been linked to increased depressive symptoms, the directionality of this association remains unclear.ObjectiveTo examine whether there is a bidirectional association between depressive symptoms and cognitive function in English adults aged 50 years or older throughout a 16-year follow-up period.Design, Setting, and ParticipantsThis cohort study included a nationally representative sample of community-dwelling English adults aged 50 years or older. The current analysis included 8268 eligible participants with relevant data. These participants were examined every other year from 2002 and 2003 until 2018 and 2019, resulting in a follow-up period of up to 16 years. Data were analyzed from July to November 2023.Main Outcomes and MeasuresThe bivariate dual change score models were used to estimate the multivariable associations between depressive symptoms and cognitive function, which were interchangeably used as exposures and outcomes. Cognitive measures include memory and verbal fluency tests, while the Center for Epidemiologic Studies Depression Scale evaluated depressive symptoms.ResultsThe study population of 8268 participants had a mean (SD) age of 64 (10) years at the study baseline, and 4517 participants (55%) were female. Higher depressive symptoms were cross-sectionally associated with poorer memory (β intercept, −0.018; standard error [SE], 0.004; P &amp;lt; .001) and verbal fluency (β intercept, −0.009; SE, 0.004; P = .02) at study baseline. A steeper linear change in depressive symptoms was associated with an accelerated memory change (β intercept, −0.253; SE, 0.079; P = .001), and a linear change in memory was associated with an acceleration in depressive symptoms over time (β intercept, 0.016; SE, 0.006; P = .005). This bidirectional change was not observed with verbal fluency.Conclusions and RelevanceIn this study, greater depressive symptoms were associated with poorer memory at the study baseline and steeper memory change over time. A gradual linear change in depressive symptoms contributed to accelerated memory loss and vice versa, suggesting that psychological mood and memory performance are intrinsically associated.
Laterally π‐Extensed Nitrogen‐Doped Molecular Nanographenes – From Anti‐Kasha Emission to Ping‐Pong Energy Transfer Events
Authors: Beneventi Giovanni M. , Schöll Kilian , Platzer Benedikt , Krug Marcel , Mai Lukas A. , Negri Fabrizia , Cadranel Alejandro , Jux Norbert , Guldi Dirk M. 
Published: June 2024

AbstractNanographenes, which feature at least one dimension smaller than 100 nm, are drawing interdisciplinary attention. Understanding the interplay between structure and properties is, however, still in its infancy. Molecular nanographenes are much better suited to fill this knowledge gap than graphene quantum dots or nanoribbons. Their bottom‐up synthesis allows atomic precision and, thereby, assists in handling structure and connecting it with properties. Herein, the effects of nitrogen‐doping and lateral π‐extension in molecular nanographenes and in their coordination complexes with ruthenium porphyrins are investigated. The presence of just nitrogen resulted in an increase of the fluorescence quantum yield, without, however, affecting the energy levels. Lateral π‐extension of the nanographenes, instead, resulted in a modulation of the excited states energy, which leads to a thermally‐activated dual fluorescence with quantum yields as high as 61%. In the corresponding coordination complexes, lateral π‐extension resulted in a ping‐pong energy transfer cascade, that is, from the nanographene to the metalloporphyrin and back to the nanographene. The results help to directly rationalize properties observed in both graphene quantum dots and nanoribbons. Moreover, they prove that molecular nanographenes are appealing components for solar energy conversion schemes, where the modulation of inter‐component energy transfer is of utmost importance.
Low circulating tumor cell levels correlate with favorable outcomes and distinct biological features in multiple myeloma
Authors: Kostopoulos Ioannis V. , Ntanasis‐Stathopoulos Ioannis , Rousakis Pantelis , Malandrakis Panagiotis , Panteli Chrysanthi , Eleutherakis‐Papaiakovou Evangelos , Angelis Nikolaos , Spiliopoulou Vasiliki , Syrigou Rodanthi‐Eleni , Bakouros Panagiotis , Dimitrakopoulou Georgia , Fotiou Despina , Migkou Magdalini , Kanellias Nikolaos , Paschalidis Nikolaos , Gavriatopoulou Maria , Kastritis Efstathios , Dimopoulos Meletios‐Athanasios , Tsitsilonis Ourania E. , Terpos Evangelos 
Published: June 2024

AbstractThere is growing interest in multiple myeloma (MM) circulating tumor cells (CTCs), but their rareness in peripheral blood (PB) and inconsistency in cutoffs question their clinical utility. Herein, we applied next‐generation flow cytometry in 550 bone marrow (BM) and matched PB samples to define an optimal CTC cutoff for both transplant‐eligible and transplant‐ineligible newly diagnosed MM (NDMM) patients. Deep phenotyping was performed to investigate unique microenvironmental features associated with CTC dissemination. CTCs were detected in 90% of patients (median 0.01%; range: 0.0002%–12.6%) and increased levels associated with adverse features. Correlations were observed between high CTC percentages and a diffused MRI pattern, a distinct BM composition characterized by altered B‐cell differentiation together with an expansion of effector cells and tumor‐associated macrophages, as well as a greater phenotypic dissimilarity between BM and PB clonal cells. Progression‐free survival (PFS) and overall survival (OS) gradually worsened with each logarithmic increment of CTCs. Conversely, NDMM patients without CTCs showed unprecedented outcomes, with 5‐year PFS and OS rates of 83% and 97%, respectively. A cutoff of 0.02% CTCs was independent of the ISS, LDH, and cytogenetics in a multivariate analysis of risk factors for PFS. The 0.02% CTC cutoff synergized with the MGUS‐like phenotype and the R‐ISS for improving the risk stratification systems. MRD negativity was less frequent if CTCs were ≥0.02% at diagnosis, but whenever achieved, the poor prognosis of these patients was abrogated. This study shows the clinical utility of CTC assessment in MM and provides evidence toward a consensus cutoff for risk stratification.
Synthese und Charakterisierung eines Kupfer‐Distickstoff‐Komplexes unter Verwendung eines schwach koordinierenden Anions
Authors: Willrett Julie , Schmitt Manuel , Zhuravlev Vadim , Sellin Malte , Malinowski Przemysław J. , Krossing Ingo 
Published: June 2024

AbstractWir stellen die Synthese und vollständige Charakterisierung des Kupfer‐Distickstoff‐Komplexes [(η1‐N2)Cu{Al(ORF)4}] 2 (RF=C(CF3)3) vor, welcher durch eine Kaskaden‐Metathese‐Reaktion zwischen Ag[Al(ORF)4] und einem CuI‐Überschuss in iso‐Perfluorhexan (i‐pfh) unter N2‐Atmosphäre hergestellt wurde. Die Titelverbindung 2 weist eine außerordentlich hohe N2‐Streckschwingungsfrequenz von 2313/2314 cm−1 (IR/Raman) auf und wurde durch Einkristall‐ und Pulver‐Röntgendiffraktometrie charakterisiert. Quantenchemische Ladungsverschiebungsanalysen basierend auf natürlichen Orbitalen der chemischen Valenz (CD‐NOCV) legen nahe, dass die Kupfer‐Distickstoff‐Interaktion durch eine schwache π‐Rückbindung charakterisiert wird, welche jedoch im Vergleich zu allen literaturbekannten Übergangsmetall‐Distickstoff‐Komplexen stark abgeschwächt ist.
Dichloromethane as C1 Synthon for the Photoredox Catalytic Cyclopropanation of Aromatic Olefins
Authors: Aragón Jordi , Sun Suyun , Fernández Sergio , Lloret‐Fillol Julio 
Published: June 2024

AbstractDichloromethane, as a readily available and inexpensive C1 synthon is proposed as a powerful building block for cyclopropanation of alkenes under mild conditions. Herein, we report a highly efficient and versatile dual photoredox system, involving a nickel aminopyridine coordination complex and a photocatalyst, for the cyclopropanation of aromatic olefins using dichloromethane, under visible‐light irradiation. The cyclopropanation protocol has been successfully applied at gram scale. Mechanistic studies suggest a Ni(II) pyridyl radical complex as the key intermediate for the homolytic cleavage of the Csp3−Cl bond, generating a chloromethyl radical that is captured by the olefin coupling partner. Our findings also highlight the versatility of this methodology. By directing the radical/polar crossover process, we were able to selectively drive the reaction towards either the formation of cyclopropyl derivatives or the corresponding non‐cyclic alkyl chloride products. The methodology also successfully apply to geminal dichloroalkanes, including the formation of spiro[2,2] compounds. Moreover, our methodology extends to the synthesis of deuterium‐labelled cyclopropanes, demonstrating its utility in isotopic labelling and broadening its applicability in chemical synthesis and drug development.
Expedited Synthesis of Metal Phosphides Maximizes Dispersion, Air Stability, and Catalytic Performance in Selective Hydrogenation
Authors: Karam Leila , Farès Christophe , Weidenthaler Claudia , Neumann Constanze N. 
Published: June 2024

AbstractMetal phosphides have been hailed as potential replacements for scarce noble metal catalysts in many aspects of the hydrogen economy from hydrogen evolution to selective hydrogenation reactions. But the need for dangerous and costly phosphorus precursors, limited support dispersion, and low stability of the metal phosphide surface toward oxidation substantially lower the appeal and performance of metal phosphides in catalysis. We show here that a 1‐step procedure that relies on safe and cheap precursors can furnish an air‐stable Ni2P/Al2O3 catalyst containing 3.2 nm nanoparticles. Ni2P/Al2O3 1‐step is kinetically competitive with the palladium‐based Lindlar catalyst in selective hydrogenation catalysis, and a loading corresponding to 4 ppm Ni was sufficient to convert 0.1 mol alkyne. The 1‐step synthetic procedure alters the surface ligand speciation of Ni2P/Al2O3, which protects the nanoparticle surface from oxidation, and ensures that 85 % of the initial catalytic activity was retained after the catalyst was stored under air for 1.5 years. Preparation of Ni2P on a variety of supports (silica, TiO2, SBA‐15, ZrO2, C and HAP) as well as Co2P/Al2O3, Co2P/TiO2 and bimetallic NiCoP/TiO2 demonstrates the generality with which supported metal phosphides can be accessed in a safe and straightforward fashion with small sizes and high dispersion.
Synthesis and Characterization of a Copper Dinitrogen Complex Supported by a Weakly Coordinating Anion
Authors: Willrett Julie , Schmitt Manuel , Zhuravlev Vadim , Sellin Malte , Malinowski Przemysław J. , Krossing Ingo 
Published: June 2024

AbstractWe report the synthesis and full characterization of the copper dinitrogen complex [(η1‐N2)Cu{Al(ORF)4}] 2 (RF=C(CF3)3) prepared by a cascade metathesis reaction of Ag[Al(ORF)4] with CuI‐excess in iso‐perfluorohexane (i‐pfh) under N2 atmosphere. Title compound 2 features an extraordinarily high N2 stretching frequency at 2313/2314 cm−1 (IR/Raman) and was characterized by single‐crystal and powder X‐ray diffractometry. Quantum chemical charge displacement analysis based on natural orbitals of chemical valence (CD‐NOCV) indicates that the copper‐dinitrogen interaction is still governed by weak π‐backdonation, but is significantly reduced compared to all literature‐known transition metal dinitrogen complexes.
Photoactivated Circularly Polarized Room‐Temperature Phosphorescence from Phenoselenazine Derivative and Its Application in Information Security†
Authors: Fu Shiyao , Chen Yi , Xie Yujun , Li Zhen 
Published: June 2024

Comprehensive SummaryRoom‐temperature phosphorescence (RTP) materials have experienced rapid development due to their potential in organic light‐ emitting diode, information security, bioimaging, etc. However, the design of chiral organic phosphors with circularly polarized RTP (CPP) property remains a formidable challenge. Here, we introduce a chiral perturbation approach using a combination of chiral binaphthol and phenoselenazine derivative to achieve CPP. The photoactivated CPP in polystyrene (PS) film demonstrates a luminescence dissymmetry factor (glum), emission efficiency, and RTP lifetime up to 9.32 × 10–3, 27.0%, and 40.0 ms, respectively. The remarkable sensitivity of PS film to oxygen and temperature enables the adjustable emission colors, ranging from green to offwhite and blue under varying conditions. The doping systems, utilizing hosts of triphenylphosphine and 9‐phenylcarbazole, demonstrate an extended CPP lifetime of 85.9 ms and exhibit a persistent mechanoluminescence property with low pressure response threshold as low as 0.15 N. The information security provided by this CPP material was attained via the using of diverse emission colors and afterglow generated by distinct UV irradiation times and host materials. Alternately, it can also be achieved by observing different emission patterns using R‐ and L‐polarizer. The research has presented a reliable approach for producing CPP materials with high emission efficiency and glum.
Clinical Translation of Inorganic Nanoparticles and Engineered Living Materials for Cancer Therapy
Authors: Gandarias Lucía , Faivre Damien 
Published: June 2024

AbstractA wide range of particle‐based nano‐ to microsystems is currently under investigation for potential use in personalized nanomedicine. However, only a small fraction of these innovations is likely to make it to clinical use. In this concept article, we start by discussing the potential applications of inorganic nanoparticles in cancer treatment and diagnosis, and shed light on the challenges they must overcome to become clinically available. In the second part, we focus on engineered living materials, which have begun to revolutionize the way medical interventions could be performed. Finally, we share our insights and opinions to explain why, despite significant advancements in research on these technologies, their translation to clinical practice remains limited.
Design Strategy for the Synthesis of Self‐Doped n‐Type Molecules
Authors: Wang Cheng , Guo Kai , Deng Yunfeng , Geng Yanhou 
Published: June 2024

Abstractn‐Type organic conductive molecules play a significant role in organic electronics. Self‐doping can increase the carrier concentration within the materials to improve the conductivity without the need for additional intentional dopants. This review focuses on the various strategies employed in the synthesis of self‐doped n‐type molecules, and provides an overview of the doping mechanisms. By elucidating these mechanisms, the review aims to establish the relationship between molecular structure and electronic properties. Furthermore, the review outlines the current applications of self‐doped n‐type molecules in the field of organic electronics, highlighting their performance and potential in various devices. It also offers insights into the future development of self‐doped materials.
Photoelectrocatalytic Reduction of Nitrobenzene to Azobenzene by Using Ag Nanoparticles‐Decorated Si Nanocone Arrays Photocathodes
Authors: Zhang Kai , Yu Jiacheng , Ru Changzhou , Mu Lixuan , Li Junjie , Shi Wensheng , She Guangwei 
Published: June 2024

AbstractPhotoelectrocatalytic (PEC) reduction of nitrobenzene (NB) is an extremely promising technology for renewable energy utilization and conversion. PEC reduction of NB to produce higher‐value azobenzene (AZB) instead of aniline (AN), which is now commonly reported, is not currently achievable. In this work, we fabricated Ag nanoparticles (AgNPs)‐decorated silicon nanocone (SiNC) array photocathodes with which the PEC reduction of NB to azobenzene (AZB) was realized for the first time. The SiNC array structure constructed by cryogenic dry etching greatly improved the light absorption ability of the photoelectrode. Ag was chosen as the cocatalyst because of its larger potential difference for the NB reduction reaction and the competing side reaction hydrogen evolution reaction. The Schottky junction formed by AgNPs with Si facilitates the rapid extraction of photogenerated electrons to participate in the PEC reaction. Under the optimized conditions, the PEC reduction of NB was achieved with a conversion of more than 90 %, with the reduction products being mainly AZB (9 : 1 ratio of AZB to AN) as well as excellent stability. The present work provides a photoelectrode that highly selectively PEC reduction of NB to AZB, and also provides insights into the design and preparation of high‐performance silicon‐based photoelectrodes.
Advanced electrocatalysts for fuel cells: Evolution of active sites and synergistic properties of catalysts and carrier materials
Authors: Kong Zhijie , Wu Jingcheng , Liu Zhijuan , Yan Dafeng , Wu Zhi‐Peng , Zhong Chuan‐Jian 
Published: June 2024

AbstractProton exchange‐membrane fuel cell (PEMFC) is a clean and efficient type of energy storage device. However, the sluggish reaction rate of the cathode oxygen reduction reaction (ORR) has been a significant problem in its development. This review reports the recent progress of advanced electrocatalysts focusing on the interface/surface electronic structure and exploring the synergistic relationship of precious‐based and non‐precious metal‐based catalysts and support materials. The support materials contain non‐metal (C/N/Si, etc.) and metal‐based structures, which have demonstrated a crucial role in the synergistic enhancement of electrocatalytic properties, especially for high‐temperature fuel cell systems. To improve the strong interaction, some exciting synergistic strategies by doping and coating heterogeneous elements or connecting polymeric ligands containing carbon and nitrogen were also shown herein. Besides the typical role of the crystal surface, phase structure, lattice strain, etc., the evolution of structure‐performance relations was also highlighted in real‐time tests. The advanced in situ characterization techniques were also reviewed to emphasize the accurate structure‐performance relations. Finally, the challenge and prospect for developing the ORR electrocatalysts were concluded for commercial applications in low‐ and high‐temperature fuel cell systems.
The impact of ChatGPT on teaching and learning in higher education: Exploring the dual perspectives of participants who were students and teachers
Authors: Fuller Michele , Barnes Neil 
Published: June 2024

AbstractThis study explored the perceived impact of integrating Generative Artificial Intelligence Systems (GenAI) such as ChatGPT into a postgraduate Master of Education program, drawing on the dual perspectives of participants who were students and educators teaching students at different levels of education in England. Using the Situated Expectancy‐Value Theory and Activity‐Centered Analysis and Design theoretical frameworks, the findings revealed opportunities, benefits, and challenges. Benefits included personalized learning and efficiencies in course design while the challenges consisted of ethical concerns, holistic skill development and problem solving. The surprising outcome of this study was the strong emotive anxiety around using AI and GenAI in participants’ academic and personal lives. A balanced, critically reflective approach can help realize ChatGPT's educational potential while navigating implementation barriers and associated challenges. Participants insights can add to the dialogue negotiating ways of effectively integrating GenAI into the higher education curriculum.Practical Takeaways
Foster collaboration: Educators and students should work together to develop critical evaluation skills, ethical frameworks, and adaptive strategies for responsible GenAI use.
Prioritize ethical considerations: Promote ongoing reflection on the personal and academic implications of GenAI, including potential biases and impacts on equity.
Balance innovation with traditional skills: Emphasize that GenAI augments, rather than replaces, core academic skills like critical thinking, source verification, and effective communication.
Align with student values: To sustain engagement, connect GenAI's use with students' immediate goals, future aspirations, and the potential to improve their learning experiences and outcomes.
Artificial intelligence and advanced data analytics: Implications for higher education
Authors: Webber Karen L. , Zheng Henry Y. 
Published: June 2024

AbstractRecently, the rise of generative AI tools such as ChatGPT have prompted deep and wide considerations about teaching and learning, student success, research and development, and the use of data for informed institutional decision making. In this volume, authors discuss specific concepts, considerations for use, and some specific tools and applications of advanced data analytics and artificial intelligence that are gaining prominence in higher education. Although these tools and our perceptions about the tools will continue to evolve, we believe that aspects of advanced data analytics and artificial intelligence will remain in our midst in the future. We believe that members of our community will become better educators and higher education managers as we engage deeply with these tools, stay vigilant about the risks and limitations, and establish policies that ensure student and institution success.Practical Takeaways
The soaring interest in aspects of artificial intelligence (AI) prompts consideration of its potential applications, impact, and implications for the higher education community.
AI‐supported tools hold the promise to help students learn more efficiently and effectively as well as assist faculty and staff with more mundane tasks, yet getting to the place where GenAI helps will take some effort. Since we must consider data privacy, ethical use, security, and accountability, the path may not be straight and narrow.
Analytics through AI tools have a particular promise to support underrepresented and disabled students through focused websites, learning support, and customized tutoring. AI has the potential to narrow the gap in student success, but without focused attention, it could serve to widen the gap across some student groups.
We acknowledge that perceptions about and implications due to artificial intelligence in higher education will change as we move forward; the articles in this volume seek to contribute to the current discussion and may prompt considerations for future conversations.