bluuebunny/crossref_metadata_2025_split huggingface dataset:
“How handy was early hominin ‘know‐how’?” An experimental approach exploring efficient early stone tool use
Authors: Eteson Brienna , Affinito Simona , Moos Elena T. , Karakostis Fotios Alexandros 
Published: September 2024

AbstractObjectivesThe appearance of early lithic industries has been associated with the gradual development of unique biomechanical and cognitive abilities in hominins, including human‐like precision grasping and basic learning and/or communicating capacities. These include tools used for activities exclusively associated with hominin contexts (cutting flakes) and hammerstones utilized for behaviors shared with non‐human primates (e.g., nut‐cracking). However, no previous experimental research has focused on comparing the factors affecting efficiency between these two key behavioral patterns and their evolutionary implications.Materials and MethodsHere, we address this gap with an experimental design involving participants with varying tool‐related experience levels (i.e., no experience, theoretical‐only experience, and extensive practical knapping expertise) to monitor their success rates, biometrics, and surface electromyography (sEMG) recordings from eight important hand and forearm muscles.ResultsOur results showed that practical experience had a substantial impact on flake‐cutting efficiency, allowing participants to achieve greater success rates with substantially less muscle effort. This relationship between success rates and muscle effort was not observed for the nut‐cracking task. Moreover, even though practical experience did not significantly benefit nut‐cracking success, experts exhibited increased rates of self‐improvement in that task.DiscussionAltogether, these experimental findings suggest that the ability to practice and retain tool‐using knowledge played a fundamental role in the subsistence strategies and adaptability of early hominins, potentially providing the cognitive basis for conceptualizing the first intentional tool production strategies.
Considering the animating ethos of designing digital first unemployment services: On the motivation of others
Authors: Griffin Ray , Jordan Antoinette , Tuite Aisling 
Published: September 2024

AbstractThis paper explores the animating ethos of digital unemployment services. Unlike human‐to‐human services, where the intention of policy is normally mediated by professionals, digital services are fully designed in the policy imagination. As a result, it is a pressing issue to understand the ethos that animates their development. To address this, we report on design thinking focus groups undertaken to support the development of a disruptive digital unemployment service that sought the views and responses of three different groups—senior policymakers, caseworkers and unemployed people in four European countries. Without prompting, each conversation variously problematised the imputed motivations of unemployed people, suggesting a form of paternalistic motivation that should only risked in‐person. From this, we suggest that the design of digital unemployment services may well be dominated by the axiomatic, uncritical mobilisation of motivation theory. Going further, we offer a brief genealogy of the form of motivation theory that surfaced in the study, highlighting its interesting, shared history in seminal studies on unemployment. As a result, we conclude, that rather than altering welfare, digitisation may reanimate, essentialise and make durable activation in new ways that deepen longstanding processes of “double activation”—activating public employment services as well as the unemployed.
The ADNI4 Digital Study: A novel approach to recruitment, screening, and assessment of participants for AD clinical research
Authors: Miller Melanie J. , Diaz Adam , Conti Catherine , Albala Bruce , Flenniken Derek , Fockler Juliet , Kwang Winnie , Sacrey Diana Truran , Ashford Miriam T. , Skirrow Caroline , Weston Jack , Fristed Emil , Farias Sarah Tomaszewski , Korecka Magda , Wan Yang , Aisen Paul S. , Beckett Laurel , Harvey Danielle , Lee Edward B. , Petersen Ronald C. , Shaw Leslie M. , Okonkwo Ozioma C. , Mindt Monica Rivera , Weiner Michael W. , Nosheny Rachel L. ,   Alzheimer's Disease Neuroimaging Initiative
Published: September 2024

AbstractINTRODUCTIONWe evaluated preliminary feasibility of a digital, culturally‐informed approach to recruit and screen participants for the Alzheimer's Disease Neuroimaging Initiative (ADNI4).METHODSParticipants were recruited using digital advertising and completed digital surveys (e.g., demographics, medical exclusion criteria, 12‐item Everyday Cognition Scale [ECog‐12]), Novoic Storyteller speech‐based cognitive test). Completion rates and assessment performance were compared between underrepresented populations (URPs: individuals from ethnoculturally minoritized or low education backgrounds) and non‐URPs.RESULTSOf 3099 participants who provided contact information, 654 enrolled in the cohort, and 595 completed at least one assessment. Two hundred forty‐seven participants were from URPs. Of those enrolled, 465 met ADNI4 inclusion criteria and 237 evidenced possible cognitive impairment from ECog‐12 or Storyteller performance. URPs had lower ECog and Storyteller completion rates. Scores varied by ethnocultural group and educational level.DISCUSSIONPreliminary results demonstrate digital recruitment and screening assessment of an older diverse cohort, including those with possible cognitive impairment, are feasible. Improving engagement and achieving educational diversity are key challenges.Highlights
A total of 654 participants enrolled in a digital cohort to facilitate ADNI4 recruitment.
Culturally‐informed digital ads aided enrollment of underrepresented populations.
From those enrolled, 42% were from underrepresented ethnocultural and educational groups.
Digital screening tools indicate > 50% of participants likely cognitively impaired.
Completion rates and assessment performance vary by ethnocultural group and education.
Targeting STAT3 signaling pathway by curcumin and its analogues for breast cancer: A narrative review
Authors: Golmohammadi Maryam , Zamanian Mohammad Yassin , Al‐Ani Ahmed Muzahem , Jabbar Thaer L. , Kareem Ali Kamil , Aghaei Zeinab Hashem , Tahernia Hossein , Hjazi Ahmed , Jissir Saad Abdul‐ridh , Hakimizadeh Elham 
Published: September 2024

AbstractBackgroundBreast cancer (BC) continues to be a significant global health issue, with a rising number of cases requiring ongoing research and innovation in treatment strategies. Curcumin (CUR), a natural compound derived from Curcuma longa, and similar compounds have shown potential in targeting the STAT3 signaling pathway, which plays a crucial role in BC progression.AimsThe aim of this study was to investigate the effects of curcumin and its analogues on BC based on cellular and molecular mechanisms.Materials & MethodsThe literature search conducted for this study involved utilizing the Scopus, ScienceDirect, PubMed, and Google Scholar databases in order to identify pertinent articles.ResultsThis narrative review explores the potential of CUR and similar compounds in inhibiting STAT3 activation, thereby suppressing the proliferation of cancer cells, inducing apoptosis, and inhibiting metastasis. The review demonstrates that CUR directly inhibits the phosphorylation of STAT3, preventing its movement into the nucleus and its ability to bind to DNA, thereby hindering the survival and proliferation of cancer cells. CUR also enhances the effectiveness of other therapeutic agents and modulates the tumor microenvironment by affecting tumor‐associated macrophages (TAMs). CUR analogues, such as hydrazinocurcumin (HC), FLLL11, FLLL12, and GO‐Y030, show improved bioavailability and potency in inhibiting STAT3, resulting in reduced cell proliferation and increased apoptosis.ConclusionCUR and its analogues hold promise as effective adjuvant treatments for BC by targeting the STAT3 signaling pathway. These compounds provide new insights into the mechanisms of action of CUR and its potential to enhance the effectiveness of BC therapies.
Hemilabile and Redox‐Active Quinone Ligands Unlock sp3‐Rich Couplings in Nickel‐Catalyzed Olefin Carbosulfenylation
Authors: Li Zi‐Qi , Alturaifi Turki M. , Cao Yilin , Joannou Matthew V. , Liu Peng , Engle Keary M. 
Published: September 2024

AbstractA three‐component coupling approach toward structurally complex dialkylsulfides is described via the nickel‐catalyzed 1,2‐carbosulfenylation of unactivated alkenes with organoboron nucleophiles and alkylsulfenamide (N−S) electrophiles. Efficient catalytic turnover is facilitated using a tailored N−S electrophile containing an N‐methyl methanesulfonamide leaving group, allowing catalyst loadings as low as 1 mol %. Regioselectivity is controlled by a collection of monodentate, weakly coordinating native directing groups, including sulfonamides, amides, sulfinamides, phosphoramides, and carbamates. Key to the development of this transformation is the identification of quinones as a family of hemilabile and redox‐active ligands that tune the steric and electronic properties of the metal throughout the catalytic cycle. Density functional theory (DFT) results show that the duroquinone (DQ) ligand adopts different coordination modes in different stages of the Ni‐catalyzed 1,2‐carbosulfenylation‐binding as an η6 capping ligand to stabilize the precatalyst/resting state and prevent catalyst decomposition, binding as an X‐type redox‐active durosemiquinone radical anion to promote alkene migratory insertion with a less distorted square planar Ni(II) center, and binding as an L‐type ligand to promote N−S oxidative addition at a relatively more electron‐rich Ni(I) center.
Curvature‐Induced Electron Spin Catalysis with Carbon Spheres
Authors: Qiao Zirui , Cao Huaqiang , Wang Jiadao , Yang Haijun , Yao Wenqing , Wang Jiaou , Cheetham Anthony K. 
Published: September 2024

AbstractHere, we report curvature‐induced electron spin catalysis by using solid carbon spheres as catalysts, which were synthesized using positive curvature molecular hexabromocyclopentadiene as a precursor molecule, following a radical coupling mechanism. The curvature spin of carbon is regarded as an overlapping state of σ‐ and π‐radical, which is identified by the inverse Laplace transform of pulse‐electron paramagnetic resonance. The growth mechanism of carbon spheres abiding by Kroto's model, is supported by the density functional theory study of thermodynamics and kinetics calculations. The solid carbon spheres present excellent catalytic behaviour of oxidation coupling of amines to form corresponding imines with the conversion of >99 %, selectivity of 98.7 %, and yield of 97.7 %, which is attributed to the predominantly curvature‐induced electron spin catalysis of carbon, supported by the calculation of oxygen adsorption energy. This work proposes a view of curvature‐induced spin catalysis of carbon, which opens up a research direction for curvature‐induced electron spin catalysis.
Development of Controllable Hetero‐Pauson‐Khand Polymerization to Functional Stimuli‐Responsive Poly(γ‐lactam)s
Authors: Du Wutong , Liu Xinyue , Sun Feiyi , Lam Jacky W. Y. , Yang Jinglei , Tang Ben Zhong 
Published: September 2024

AbstractPolymers containing lactam structures play a crucial role in both natural biological systems and human life, and their synthesis, functions and applications are of utmost importance for biomimetics and the creation of new materials. In this study, we developed an efficient heterogeneous Pauson–Khand polymerization (h‐PKP) method for the controlled synthesis of main‐chain poly(γ‐lactam)s containing α, β‐unsaturated γ‐lactam functionalities using readily available internal alkynes and imines. The molecular weights of the resulting poly(N−Ts/γ‐lactam)s can be precisely controlled by adjusting the ratio of phenyl formate and nickel. These polymers exhibit high solid‐state luminescence and demonstrate rapid and sensitive dual responsiveness to light and acid stimuli. They further demonstrate strong reactive oxygen species (ROS) generation capability. The unique dual‐emission peaks observed in poly(N−H/γ‐lactam)s obtained through post‐treatment under acidic conditions demonstrate a mechanism of aggregation‐induced intermolecular excited‐state proton transfer specific to lactam structures. The efficient one‐pot synthetic method for poly(γ‐lactam) provides a novel strategy for constructing polymers with γ‐lactam structures in the main chain and the simple and efficient post‐modification method offer a versatile toolbox for functionalizing poly(γ‐lactam)s to expand their potential applications.
Calibrating the Oxidative Capacity of Microdroplets
Authors: Majumder Tirthick , Eremin Dmitry B. , Delibas Berk , Sarkar Archishman , Fokin ValeryV. , Dawlaty Jahan M. 
Published: September 2024

AbstractRecently, redox chemical transformations have been reported to occur spontaneously in microdroplets. The origins of such novel reactivity are still debated, and any systematic correlation of the oxidative/reductive yield with the reactivity of the reactant is yet to be established. Towards this end, we report the simple, outer‐sphere, one‐electron oxidation of a series of ferrocene derivatives spanning a range of oxidation potentials from −0.1 V to +0.8 V vs. Ag/AgCl in acetonitrile microdroplets generated via nebulization and measured by mass spectrometry of the corresponding ferrocenium ions. The reaction environments and dynamics in the droplets are complex, and it is still unclear whether such reactivity correlates with any bulk thermodynamic values. Our key finding is that the ion yields decrease monotonically with the oxidation potential of the ferrocenes, which is a thermodynamic quantity. The ion yields emphatically do not obey the Nernstian ratio, revealing the redox processes in the droplets do not follow the assumptions of bulk steady‐state electrochemistry. Furthermore, oxidative competition in the mixture of several ferrocenes suggest a finite oxidative capacity or oxidant concentration. These results demonstrate that even though ion generation could be an out‐of‐equilibrium and kinetically limited process, the oxidative yield in microdroplets does correlate with thermodynamics, suggesting a possible free energy relationship between the kinetics and thermodynamics of the process.
Highly Selective Synthesis of Acetic Acid from Hydroxyl‐Mediated Oxidation of Methane at Low Temperatures
Authors: Wu Bo , Yin Haibin , Ma Xinlong , Liu Rongjia , He Bingxuan , Li Hongliang , Zeng Jie 
Published: September 2024

AbstractDirect methane conversion and, in particular, the aerobic oxidation to acetic acid, remain an eminent challenge. Here, we reported a zeolite‐supported Au−Fe catalyst (Au−Fe/ZSM‐5) that converted methane to acetic acid with molecular oxygen as an oxidant in the presence of CO. Specifically, Au nanoparticles catalyzed the formation of hydroxyl species from the reaction of CO, O2, and H2O, meanwhile ZSM‐5‐supported atomically dispersed Fe species were responsible for the hydroxyl‐mediated coupling of CH4 and CO to generate acetic acid. The reaction over 50 mg of Au−Fe/ZSM‐5 under 62 bar (CH4 : CO : O2=14 : 14 : 3) at 120 °C for 3.0 h yielded 5.7 millimoles of acetic acid per gram of the catalyst (mmol gcat−1) with the selectivity of 92 %, outperformed most of reported catalysts. Significantly, the catalyst remained active even at 60 °C. We anticipate that this hydroxyl‐mediated route may guide the design of optimized catalysts for the direct methane functionalization at low temperatures.
A Pyridazine‐Based Cadmium(II) Organic Framework With pcu Topology as a Luminance Sensor to Nitrobenzene, Al(III), and Cu(II) Ion
Authors: Pei‐Pei Huang , Ting‐Ting Wu , Meng‐Qi Tuo , Rui‐Ying Zhang , Chun‐Jiang Shuai , Bo Liu , Juan Song , Sheng‐Rui Zhang , Jiu‐Fu Lu 
Published: September 2024

ABSTRACTIn the field of water decontamination, the design of luminance sensor for sensitive detection of heavy metal ion toxic and nitroaromatic compounds are important and challenging. Herein, a new luminescent Cd(II) metal–organic framework (MOF), {[Cd2(H2O)3(4‐CPCA)2]·2H2O}n (SNUT‐27) (H2(4‐CPCA) = 1‐(4‐carboxyphenyl)‐4‐oxo‐1,4‐dihydropyridazine‐3‐carboxylic acid) was obtained by the reaction of flexible ligand H2(4‐CPCA) and Cd(II) ions, characterized by single crystal X‐ray diffraction, PXRD, FT‐IR, and TGA, the samples were further analyzed. The analysis of single crystal X‐ray diffraction showed that SNUT‐27 possesses a distinct three‐dimensional spatial arrangement and demonstrates impressive fluorescence properties. Particularly, SNUT‐27 showed a highly sensitive response to the nitro‐aromatic compounds nitrobenzene by fluorescence quenching, and in contrast, showed a fluorescence enhancement response to Al3+ and Cu2+. SNUT‐27 can be effortlessly recycled by simply rinsing with water post‐sensing experiments, showcasing its reusability. Additionally, potential detection mechanisms have been explored.
Fabrication and performance evaluation of polycarbonate/polyvinyl alcohol–titanium dioxide thin‐film nanocomposite membranes for water treatment
Authors: Samiei Arian , Khezraqa Homayun , Etemadi Habib , Shokri Elham 
Published: September 2024

AbstractIn recent years, there has been growing interest in using polymer nanocomposite membranes as a more advanced method for removing pollutants from water and treating wastewater for various purposes. In this study, thin‐film nanocomposite (TFN) membranes of polycarbonate/polyvinyl alcohol–titanium dioxide thin‐film (PC/PVA–TiO2) were fabricated by dip‐coating a PC substrate in a PVA/TiO2 solution. Various methods, including attenuated total reflectance‐Fourier transform infrared (ATR‐FTIR) spectroscopy, field emission scanning electron microscopy (FE‐SEM), atomic force microscopy (AFM), and water contact angle were utilized to assess the structural characteristics of the produced membranes. The PC/PVA thin‐film composite (TFC) and PC/PVA–TiO2 TFN membranes were then examined in a submerged membrane system to evaluate their effectiveness in filtering humic acid (HA) under various vacuum transmembrane pressure (0.3 and 0.6 bar) condition. The FTIR‐ATR results confirmed the formation of the active layer of PVA/TiO2 nanoparticles (NPs). It was observed that adding 1 wt.% of TiO2 NPs to the active layer of PVA/TiO2 significantly enhanced the water contact angle from 77.5° for PC support to 55.3° for PC/PVA–TiO2 (0.1) TFN membranes. Furthermore, the FE‐SEM results confirmed the formation of an active layer of PVA/TiO2 with a thickness of 237.87 nm. The pure water flux increased from 101.64 L/m2h for the PC/PVA TFC membrane to 144.02 L/m2h and 199.09 L/m2h for the PC/PVA–TiO2 (0.05) and PC/PVA–TiO2 (0.1) TFN membranes, respectively. Also, the results revealed that at lower transmembrane pressure, all membranes showed higher value in HA removal as compared to when higher transmembrane pressure was used.
Mixing screw design and high density polyethylene toughening modification for recycled polypropylene based on screw 3D printing
Authors: Zhang Yi , Bai Haiqing , Mi Dashan , Zhang Le , Jiang Jinghua , Yang Tao , Ren Zekang 
Published: September 2024

AbstractThe recycling of waste plastics primarily involves physical modification and the addition of modifiers, often utilizing equipment such as twin‐screw extruders for miscible modification. Considering the widespread use of single‐screw 3D printing, improving the mixing efficiency of the single‐screw is crucial to achieve a “one‐stop” recycling modification that is suitable for 3D printing. This paper introduces a 3D printer equipped with a mixing screw (MS) and compares it with a conventional screw (CS). We conduct numerical simulations to investigate the pressure build‐up capacity, velocity streamline distribution, and the mixing effect of the MS. The mechanical properties, thermal characteristics, and molecular orientation of the recycled Polypropylene (rPP) and high density polyethylene (HDPE) mixture are investigated through experiments. The results show that the MS provides more effective elongational flows compared to the CS by breaking down the reinforcing materials into smaller particles. Additionally, toughening and modification experiments are performed on rPP and HDPE. The composites treated with the MS showed improved elongation at break (increased by ~111%), a stable melt crystallization temperature, and an enhanced mixing effect. This study on single‐screw 3D printers lays the groundwork for streamlining the plastic recycling process and increasing the reuse rate of recycled plastics.
Synthesis of Rare Earth Metal Complexes Stabilized by Amine Bridged Bis(phenolato) Ligands and Their Performance in the Polymerization of rac‐β‐Butyrolactone
Authors: Shi Yize , Wang Yanwei , Yuan Dan , Yao Yingming 
Published: September 2024

AbstractA series of rare earth alkoxides bearing amine‐bridged bis(phenolato) ligands were synthesized through sequential reactions of RE(C5H5)3(THF) (RE = Y, Lu) or Nd[N(SiMe3)2]3 with bis(phenols) LH2 and CF3CH2OH. Complexes REL(OCH2CF3)(THF)n (1–6) bearing different aryl‐substituents were obtained in good yields of 59–70 %. They were applied in the ring‐opening polymerization (ROP) of rac‐β‐butyrolactone (rac‐BBL), which showed good activity (TOF up to 27,300 h−1), resulting in syndiotactically enriched poly(3‐hydroxybutyrate) (PHB) (Pr up to 0.86) with narrow polydispersities (PDI ≤ 1.27). The yttrium complex 3 bearing bulky o‐1,1‐diphenylethyl substituents outperformed other complexes, suggesting that the smaller ionic radii of metal centers and bulky ortho substituents of ancillary ligands play crucial roles in controlling the activity and stereoselectivity in ROP of rac‐BBL. Kinetics of the polymerization of rac‐BBL initiated by complex 3 was investigated, which revealed first order dependences on the monomer and initiator concentrations, respectively.
hsa_circ_0000129 targets miR‐383‐5p/tropomyosin 3 axis to facilitate ovarian cancer progression
Authors: Li Yuan , Liu Can 
Published: September 2024

AbstractOvarian cancer is one of the most prevalent malignancies among women. CircRNAs play key roles in the progression of ovarian cancer. This study aimed to investigate the mechanism of action of hsa_circ_0000129 and its effects on ovarian cancer. Expression of hsa_circ_0000129, tropomyosin 3 (TPM3), and miR‐383‐5p in ovarian cancer cell lines and tissue specimens was detected using qRT‐PCR or western blotting. Cell counting kit‐8 (CCK‐8), colony formation, and transwell assays were performed to assess viability, proliferation, and migration of ovarian cancer cells. A xenograft model was used to study tumorigenicity of ovarian cancer cells in vivo. Luciferase and RNA immunoprecipitation assays were performed to determine binding between miR‐383‐5p and hsa_circ_0000129 or TPM3. Upregulation of hsa_circ_0000129 and TPM3 and downregulation of miR‐383‐5p were observed in ovarian cancer. Low hsa_circ_0000129 and TPM3 expression repressed viability, migration, and proliferation of ovarian cancer cells. Inhibition of miR‐383‐5p had a contrary effect. Furthermore, knockdown of hsa_circ_0000129 restricted the tumorigenicity of ovarian cancer cells. Mechanistically, hsa_circ_0000129 has a sponging effect on miR‐383‐5p, which targets TPM3. Hsa_circ_0000129 stimulated development of the malignant ovarian cancer phenotype by sponging miR‐383‐5p and releasing TPM3.