bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electrochemical and Optical Spectroscopic Probing of Transition‐Sized Au130(SR)50 Nanoclusters
Authors: Du Xiangsha , Zhang Xinwen , Ma Hedi , Zhou Meng , Higaki Tatsuya , Wang Gangli , Wang He , Jin Rongchao 
Published: March 2024

AbstractUltrasmall metal nanoclusters (NCs) exhibit a quantized conduction band, hence, a distinct HOMO‐LUMO gap (Eg). Such a quantized electronic structure gives rise to multiple discrete peaks in the optical absorption spectrum of the NCs. As the size grows to 130 gold atoms (Au130 protected by ligands), electrical charging and optical behaviors seem to show certain metal‐like features (hence, transition‐sizes). To probe such behaviors, especially the potential ligand effect, we have devised the synthesis of Au130 NCs protected by phenylethanethiolate and naphthalenethiolate, respectively, with the former having a nonconjugated separation between the aromatic molecular group and the metal core while the latter being in direct bonding. A careful comparison of these two Au130 nanoclusters with the earlier reported analogues is carried out, including the structurally characterized Au130(pMBT)50 and the aqueous counterpart. While all of these nanoclusters possess the same 80 free electron counts in the core, some notable differences in electrochemical and optical properties are found, which are attributed to the ligand effects. The obtained insights may stimulate further interest in the transition‐sized nanoclusters and also promote their applications in optics, energy conversion, and biomedicine.
A GFP Inspired 8‐Methoxyquinoline–Derived Fluorescent Molecular Sensor for the Detection of Zn2+ by Two–Photon Microscopy
Authors: Csomos Attila , Madarász Miklós , Turczel Gábor , Cseri Levente , Bodor Andrea , Matuscsák Anett , Katona Gergely , Kovács Ervin , Rózsa Balázs , Mucsi Zoltán 
Published: March 2024

AbstractAn effective, GFP‐inspired fluorescent Zn2+ sensor is developed for two–photon microscopy and related biological application that features an 8‐methoxyquinoline moiety. Excellent photophysical characteristics including a 37‐fold fluorescence enhancement with excitation and emission maxima at 440 nm and 505 nm, respectively, as well as a high two–photon cross–section of 73 GM at 880 nm are reported. Based on the experimental data, the relationship between the structure and properties was elucidated and explained backed up by DFT calculations, particularly the observed PeT phenomenon for the turn–on process. Biological validation and detailed experimental and theoretical characterization of the free and the zinc–bound compounds are presented.
Influence of Polymer Side Chain Size and Backbone Length on the Self‐Assembly of Supramolecular Polymer Bottlebrushes
Authors: Ulrich Hans F. , Gruschwitz Franka V. , Klein Tobias , Ziegenbalg Nicole , Anh Doan Thi Ngoc , Fujii Shota , Hoeppener Stephanie , Sakurai Kazuo , Brendel Johannes C. 
Published: March 2024

AbstractHydrogen bonds are a versatile tool for creating fibrous, bottlebrush‐like assemblies of polymeric building blocks. However, a delicate balance of forces exists between the steric repulsion of the polymer chains and these directed supramolecular forces. In this work we have systematically investigated the influence of structural parameters of the attached polymers on the assembly behaviour of benzene trisurea (BTU) and benzene tris(phenylalanine) (BTP) conjugates in water. Polymers with increasing main chain lengths and different side chain sizes were prepared by reversible addition‐fragmentation chain‐transfer (RAFT) polymerization of hydroxyethyl acrylate (HEA), tri(ethylene glycol) methyl ether acrylate (TEGA) and oligo(ethylene glycol) methyl ether acrylate (OEGA). The resulting structures were analyzed using small angle X‐ray scattering (SAXS) and transmission electron microscopy (TEM). Both BTU and BTP formed fibres with PHEA attached, but a transition to spherical morphologies was observed at degrees of polymerisation (DP) of 70 and above. Overall, the main chain length appeared to be a dominating factor in inducing morphology transitions. Increasing the side chain size generally had a similar effect but mainly impeded any aggregation as is the case of POEGA. Interestingly, BTP conjugates still formed fibres, suggesting that the stronger intermolecular interactions can compensate partially for the steric repulsion.
Designing Ionic Ir(III) Cyclometalated Complexes as Photocatalysts for Light Assisted ATRP of MMA. A Combined Experimental and Mechanistic Study
Authors: Vigarani Giulia , Marchini Edoardo , Previati Eleonora , Giorgini Loris , Zacchini Stefano , Argazzi Roberto , Massi Massimiliano , Fiorini Valentina , Caramori Stefano , Stagni Stefano 
Published: March 2024

AbstractA new family of ionic Ir(III) cyclometalated complexes with general formula [Ir(CN)2(NN)][Br], was designed and prepared to be assessed as photocalysts for the visible light assisted ATRP polymerization of MMA. To this purpose, our design strategy involved both: i) the decoration of the cyclometalating (CN) and the ancillary (NN) ligands with various electron withdrawing and/or electron donor substituents and, ii) the use of Br− as the counter anion for these cationic Ir(III) species. After an extensive screening in which the [Ir(CN)2(NN)][Br]‐type compounds were compared to the model neutral complex fac‐[Ir(ppy)3], the “fully” amino‐substituted ion pairs abbreviated as [10][Br] and [11][Br], exhibited the best photocatalytic performances under irradiation with CFL lamps. It is worth noting that the outcomes of transient absorption spectroscopy (TAS) experiments combined with theoretical DFT calculations, enlightened the role played by the Ir(III) complexes in the mechanism of the photoATRP process, and suggested the rationalization of the different performances that were highlighted by our Ir(III) catalyst in the visible light assisted photopolymerization of MMA.
Bimodal Use of Chiral α‐Trifluoromethylalanine in Aib Foldamers: Study of the Position Impact Towards the Helical Screw‐Sense Preference
Authors: Picois Nathan , Bodero Lizeth , Milbeo Pierre , Brigaud Thierry , Chaume Grégory 
Published: March 2024

AbstractOligomers of the achiral α‐aminoisobutyric acid (Aib) adopt a 310 helical conformation in which the screw‐sense preference can be controlled by a single chiral residue. The use of the fluorinated residue α‐Trifluoromethylalanine (α‐TfmAla) revealed a unique way to both induce and measure the screw‐sense preference of such oligomers acting as 19F NMR probe. This work proposes a systematic study of the effect of this fluorinated chiral inducer on the helical screw‐sense preference of poly‐Aib oligomers. The impact of the position of the fluorinated residue into pentamers (N‐terminal, central or C‐terminal) as well as the nature of the C‐terminal capping of the peptides was thoroughly studied in light of complete structural analysis. A deeper understanding of the fluorine effect was achieved confirming the unique ability of α‐TfmAla as a helical screw‐sense controller.
N,N’‐Diaryl‐Sulfurdiimides are Strongly Redox Tuned
Authors: Hill Nathan D. D. , Boeré René T. 
Published: March 2024

AbstractThe synthesis and extensive characterization of nine aryl sulfur diimides (SDIs, Ar−NSN−Ar) are presented with a robust computational and experimental investigation of the fundamental properties of these important members of the thiazyl family of compounds, with particular attention paid to their highly tunable electrochemical behaviour. This is the first work to undertake a systematic comparison of the electrochemical profiles of a coherent series of SDIs to demonstrate and quantify the response of their reduction potentials to substituent electron‐donating and ‐withdrawing properties. This effect is found to be not only exceptionally strong, but also correlates very closely with computed orbital energies. Electron paramagnetic resonance spectroscopy is used to determine the nature, localization, and qualitative lifetimes of the radical anions of SDIs. This work also addresses significant misconceptions about physical properties of SDIs. Experimental data and modern computational methods are employed to provide a resolute answer to the long‐standing contention of the solution‐state conformations of SDIs, and to correct historical mistakes in the assignment of infrared spectroscopic data. High‐quality crystal structures of all SDIs in this work showcase the utility of the recently introduced structural refinement software NoSpherA2, enabling full anisotropic refinement of H‐atoms with accurate C−H bond lengths.
Copper and Copper Complexes in Tumor Therapy
Authors: Wang Yingqiao , Tang Tingxi , Yuan Yi , Li Nan , Wang Xiaoqing , Guan Jian 
Published: March 2024

AbstractCopper (Cu), a crucial trace element in physiological processes, has garnered significant interest for its involvement in cancer progression and potential therapeutic applications. The regulation of cellular copper levels is essential for maintaining copper homeostasis, as imbalances can lead to toxicity and cell death. The development of drugs that target copper homeostasis has emerged as a promising strategy for anticancer treatment, with a particular focus on copper chelators, copper ionophores, and novel copper complexes. Recent research has also investigated the potential of copper complexes in cancer therapy.
Combinatorial Libraries of Bipodal Binders of the Insulin Receptor
Authors: Selicharová Irena , Fabre Benjamin , Soledad Garre Hernández María , Lubos Marta , Pícha Jan , Voburka Zdeněk , Mitrová Katarína , Jiráček Jiří 
Published: March 2024

AbstractThe binding process of insulin to its transmembrane receptor entails a sophisticated interplay between two proteins, each possessing two binding sites. Given the difficulties associated with the use of insulin in the treatment of diabetes, despite its remarkable efficacy, there is interest in smaller and more stable compounds than the native hormone that would effectively activate the receptor. Our study adopts a strategy focused on synthesizing extensive combinatorial libraries of bipodal compounds consisting of two distinct peptides linked to a molecular scaffold. These constructs, evaluated in a resin bead‐bound format, were designed to assess their binding to the insulin receptor. Despite notable nonspecific binding, our approach successfully generated and tested millions of compounds. Rigorous evaluations via flow cytometry and specific antibodies revealed peptide sequences with specific interactions at either receptor binding Site 1 or 2. Notably, these sequences bear similarity to peptides discovered through phage display by other researchers. This convergence of chemical and biological methods underscores nature‘s beauty, revealing general principles in peptide binding to the insulin receptor. Overall, our study deepens the understanding of molecular interactions in ligand binding to the insulin receptor, highlighting the challenges of targeting large proteins with small synthetic peptides.
Iridium Nanoparticles as Highly Effective Peroxidase Mimics: Synthesis, Characterization, and Application in Biosensing
Authors: Gao Weiwei , Sun Xiaohan , Yishay Tamar , Wei Zhiyuan , Zhu Xiangyu , Kim Moon J. , Xia Xiaohu 
Published: March 2024

AbstractPeroxidase mimics made of inorganic nanomaterials as alternatives to natural peroxidases have been extensively developed over the past few decades, owing to their superior properties relative to their natural counterparts. Nevertheless, it has been still a challenge to substantially enhance the catalytic efficiency of peroxidase mimics. In this work, we report a type of highly efficient peroxidase mimics that are made of iridium nanoparticles (Ir NPs) with rough surfaces. The Ir NPs possess an ultrahigh catalytic efficiency with a catalytic constant (Kcat) at the regime of 1010 s−1, orders of magnitude higher than the Kcat of horseradish peroxidase as a natural peroxidase. As a proof‐of‐concept demonstration, the Ir NPs were applied to colorimetric lateral flow assay (CLFA). Using carcinoembryonic antigen as a model disease biomarker, the Ir NPs‐based CLFA achieved a low limit of detection (LoD) of 39 pg/mL, which was ~28 times lower than the LoD of conventional gold nanoparticles‐based CLFA using the same antibodies.
De‐politicization and corporate social responsibility: Empirical evidence from China
Authors: Qiu Yuan , Zhou Di 
Published: March 2024

AbstractGiven the lack of consensus in the existing studies about the impact of political resources on corporate social responsibility (CSR), we delve into this relationship and analyze the underlying mechanisms. To address the endogenous problems associated with political connection, this paper explores the consequence of de‐politicization and adopts an exogenous event in China. Results indicate that de‐politicization significantly enhances the CSR performance of firms. Specifically, de‐politicization can lead to a 1.474 increase in CSR scores. This finding is further supported by various robustness tests. Additionally, this paper probes into the reasons for the positive influence focusing on prerequisite and driving forces. For one thing, de‐politicization reduces the rent‐seeking expenses of politically connected firms, thereby granting these firms enough financial resources to improve their CSR performance. For another thing, CSR practices can convey positive information, improve financial performance, and enhance competitiveness, which motivates firms to actively participate in CSR issues to alleviate the adverse influence of losing political connection. This paper enriches the existing research on political connections and provides theoretical guidance and policy recommendations for improving CSR in developing countries.
The role of the cultural context in moderating the effect between the presence of women directors and firm environmental innovation
Authors: Traversi Marco , Bannò Mariasole , Filippi Emilia 
Published: March 2024

AbstractThis study examines the relationship between the presence of women in board of directors and environmental innovation and the moderating role of the cultural context in terms of gender inequality through the lens of Social Identity Theory. We measured the presence of women directors as board gender diversity, presence of only one woman director and presence of at least three women directors. We measured environmental innovation using environmental patents, also distinguishing among Air Pollution, Solid Waste, and Water Pollution. The sample consists of 2453 manufacturing firms operating in Spain, France, Italy, the Netherlands, and Germany. The Multiple Linear Regression Poisson models performed suggest that the presence of women directors do not affect or reduce environmental innovation, while gender inequality in the cultural context plays a negative moderating role. This study contributes to literature as it clarifies the previous contradictory results and investigates the moderating role of the cultural context.
An adaptive load‐matching method for the induction heating coil with DC power supply
Authors: Shami Umar Tabrez , Shami Tabrez Aslam 
Published: March 2024

SummaryThis article proposes a method to transfer maximum power from a power supply to an induction heating load by matching the dynamic resistance of the induction heating resonant circuit with the internal resistance of the power supply source. The method is to select a capacitor connected in parallel to the induction coil and tune the correct value of the inverter frequency to the induction heating circuit resonant frequency. The proposed method can be used for heating work loads with an energy‐saving purpose in induction heating applications. The switching frequency of the single‐phase full‐bridge inverter is variable so that the inverter frequency can be matched with the coil and parallel‐connected capacitor (RLC tank circuit) resonant frequencies. To demonstrate the feasibility of the load‐matching technique proposed, we experimented with two types of loads that were both stainless steel vessel containers with almost similar size and dimensions but different magnetic properties. We conducted experiments based on the proposed technique and obtained satisfactory results that supported our synopsis. The methods used to collect and analyze the data were carefully chosen and have been described in the methodology section of the research paper.
Distinct fibroblast subpopulations associated with bone, brain or intrapulmonary metastasis in advanced non‐small‐cell lung cancer
Authors: Xu Ke , Wang Hao , Zou Yu‐Xia , Zhang Huan‐Huan , Wang Yue‐Nan , Ren Xue‐Ru , Wang Han‐Qi , Xu Ye‐Hong , Li Jia‐Jun , Tang Hao , He Cheng , Wei Song , Tian Tian , Li Lai‐Lin , Zhou Hui , Xu Lin‐Juan , Fang Jing‐Wen , Guo Chuang , Yang Jia‐Xuan , Zhou You‐Yang , Zhang Zhi‐Hong , Pan Yue‐Yin 
Published: March 2024

AbstractBackgroundBone or brain metastases may develop in 20–40% of individuals with late‐stage non‐small‐cell lung cancer (NSCLC), resulting in a median overall survival of only 4–6 months. However, the primary lung cancer tissue's distinctions between bone, brain and intrapulmonary metastases of NSCLC at the single‐cell level have not been underexplored.MethodsWe conducted a comprehensive analysis of 14 tissue biopsy samples obtained from treatment‐naïve advanced NSCLC patients with bone (n = 4), brain (n = 6) or intrapulmonary (n = 4) metastasis using single‐cell sequencing originating from the lungs. Following quality control and the removal of doublets, a total of 80 084 cells were successfully captured.ResultsThe most significant inter‐group differences were observed in the fraction and function of fibroblasts. We identified three distinct cancer‐associated fibroblast (CAF) subpopulations: myofibroblastic CAF (myCAF), inflammatory CAF (iCAF) and antigen‐presenting CAF (apCAF). Notably, apCAF was prevalent in NSCLC with bone metastasis, while iCAF dominated in NSCLC with brain metastasis. Intercellular signalling network analysis revealed that apCAF may play a role in bone metastasis by activating signalling pathways associated with cancer stemness, such as SPP1‐CD44 and SPP1‐PTGER4. Conversely, iCAF was found to promote brain metastasis by activating invasion and metastasis‐related molecules, such as MET hepatocyte growth factor. Furthermore, the interaction between CAFs and tumour cells influenced T‐cell exhaustion and signalling pathways within the tumour microenvironment.ConclusionsThis study unveils the direct interplay between tumour cells and CAFs in NSCLC with bone or brain metastasis and identifies potential therapeutic targets for inhibiting metastasis by disrupting these critical cell–cell interactions.
RETRACTED: Multifactor optimized mobile sink data collection framework for hybrid wireless sensor network‐long term evolution‐assisted Internet of Things network
Authors: Mohan Saranga , Panda Sunita 
Published: March 2024

SummaryThe wireless sensor network‐assisted Internet of Things convergence has diverse applications. In most applications, the sensors are battery‐powered, and it is necessary to use the energy judiciously to extend their functional duration effectively. Mobile sinks‐based data collection is used to extend the lifespan of these networks. However, providing a scalable and effective solution with consideration for multicriteria factors of quality of service and lifetime maximization is still a challenge. This work addresses this problem with a hybrid wireless sensor network with long‐term evolution‐assisted architecture. The issue of maximizing lifetime and providing multifactor quality of service is solved as a two‐stage optimization problem involving clustering and data collection path scheduling. Hybrid meta‐heuristics is used to solve the clustering optimization problem. Minimal Steiner tree‐based graph theory is applied to schedule the data collection path for sinks. Unlike existing works, the lifetime maximization without QoS degradation is addressed by hybridizing multiple approaches of multicriteria optimal clustering, optimal path scheduling, and network adaptive traffic class‐based data scheduling. This hybridization extends the network's lifespan and improves the QoS regarding packet transmission within the proposed solution. Through simulation analysis, the introduced approach yields a noteworthy increase of at least 6% and reduces packet delivery delay by 26% compared with existing methodologies.
Navigating University Openness in Research Policy Inconsistent with Indigenous Data Sovereignty: A Case Analysis
Authors: Wick Molly , Erickson Deanna , Hoffman Joel , Johnson Lucinda , Angradi Ted 
Published: March 2024

ABSTRACTIndigenous nations and communities in the United States have rights as sovereign governments to exercise control and ownership over all data and information generated by or from the tribes, tribal members, or tribal resources. Indigenous nations exercise these rights through data ownership policies established in response to unethical research practices in research involving Indigenous communities. Most universities in the U.S. have “openness in research” policies to ensure academic freedom to publish freely, exercised by retaining university control of data. Here, we describe our study of cultural ecosystem services in the St. Louis River estuary region (Nagaajiwanaang in the language Ojibwemowin) in Duluth, Minnesota, and Superior, Wisconsin, U.S., an area that includes portions of the 1854 and 1842 Ceded Territories and reservation lands of a local band of Ojibwe (hereafter referred to as “the Band”). In this university‐led, Band‐supported study, both the university and the Band sought ownership of data collected based on their respective policies, resulting in a research delay of nearly a year. We found that open research policies that do not consider Indigenous sovereignty can hamper collaboration between university researchers and tribal nations, even when there is broad agreement on research goals and objectives. University open research policies that do not explicitly address Indigenous sovereignty fall short of the open research principles they intend to support and should be revised. Formal adoption of principles for ethical research with sovereign tribal governments by universities is needed to improve coordination and trust among university and tribal researchers and members.
Rapid Review of Therapy Protocols for Public Health Emergencies
Authors: Gordon Bruce G. , Lowe Abigail E. , Kratochvil Christopher J. 
Published: March 2024

ABSTRACTHow research during a public health emergency is conducted is recognized as essential to the public health response to that emergency. Such research needs to undergo substantive and meaningful ethical review in a timely manner. Rapid ethical review may be accomplished through a number of mechanisms, including use of local rapid‐response institutional review boards (IRBs). We describe use of such a model in the setting of the 2014 Ebola virus disease epidemic and the Rapid‐Response IRB's subsequent transition to a multisite single IRB model during the current Covid‐19 pandemic. The rapid‐response review model is characterized by a small IRB with extensive use of alternate members with specific expertise and by close collaboration with the investigator in an iterative process.