bluuebunny/crossref_metadata_2025_split huggingface dataset:
Modulating the Hydrophilic‐Hydrophobic Microenvironment of MOF‐Stabilized Pt Nanozymes: the Role of H2O in the Peroxidase‐Like Catalyzed Reaction
Authors: Shen Bingqing , Wu Qian , Guo Yanguo , Qin Jie , Chen Hailong , Yang Ying , Liu Zhenjiang , Li Longhua , Li Weibin , Zhu Chengzhou 
Published: October 2024

AbstractHydrophilicity‐hydrophobicity modulation of active sites provides a promising strategy for enhancing catalytic performance. Current researches focus on the influence of substrate molecules, however, the role of H2O molecules is often overlooked in nanozyme‐catalyzed reactions. Herein, bioinspired Pt@ZIF‐R (R = ‐90, ‐8, ‐8@TMS, where TMS is tetraethoxysilane) nanozymes are designed as model catalysts, with Pt nanoparticles as active centers and metal organic‐framework nanocavities as hydrophilic‐hydrophobic binding pockets, revealing the critical role of H2O in the peroxidase‐like catalytic process of H2O2 decomposition. A positive correlation between catalytic activity and hydrophobicity is observed, and strong hydrophobic Pt@ZIF‐8@TMS nanozyme exhibits the best catalytic performance. Theoretical calculations indicate that as hydrophobicity increases, solvent H2O reduces the competitive adsorption with H2O2 and decreases the energy barrier of the rate‐determining step (2*O→*O2) simultaneously. In addition, the desorption of the product H2O is thermodynamically favorable with increasing hydrophobicity. Importantly, Pt@ZIF‐8@TMS nanozyme is successfully used to develop a colorimetric biosensor for the detection of organophosphorus pesticides, with a detection limit as low as 0.7 ng mL−1, which is superior to numerous existing methods. This work provides fundamental insights into the function of hydrophobicity in boosting catalytic activity, which may offer guidance for the development of efficient nanozymes.
Biocompatibility of Water‐Dispersible Pristine Graphene and Graphene Oxide Using a Close‐to‐Human Animal Model: A Pilot Study on Swine
Authors: Nicolussi Paola , Pilo Giovannantonio , Cancedda Maria Giovanna , Peng Guotao , Chau Ngoc Do Quyen , De la Cadena Alejandro , Vanna Renzo , Samad Yarjan Abdul , Ahmed Tanweer , Marcellino Jeremia , Tedde Giuseppe , Giro Linda , Ylmazer Acelya , Loi Federica , Carta Gavina , Secchi Loredana , Dei Giudici Silvia , Macciocu Simona , Polli Dario , Nishina Yuta , Ligios Ciriaco , Cerullo Giulio , Ferrari Andrea , Bianco Alberto , Fadeel Bengt , Franzoni Giulia , Delogu Lucia Gemma 
Published: October 2024

AbstractGraphene‐based materials (GBMs) are of considerable interest for biomedical applications, and the pilot study on the toxicological and immunological impact of pristine graphene (GR) and graphene oxide (GO) using swine as a close‐to‐human provides valuable insights. First, ex vivo experiments are conducted on swine blood cells, then GBMs are injected intraperitoneally (i.p.) into swine. Hematological and biochemical analyses at various intervals indicate that neither GO nor GR cause systemic inflammation, pro‐coagulant responses, or renal or hepatic dysfunction. Importantly, no systemic toxicity is observed. Analysis of a panel of 84 immune‐related genes shows minimal impact of GO and GR. The animals are sacrificed 21 days post‐injection, and transient absorption imaging and Raman mapping show the presence of GO and GR in the mesentery only. Histological evaluation reveals no signs of alterations in other organs. Thus, clusters of both materials are detected in the mesentery, and GO aggregates are surrounded only by macrophages with the formation of granulomas. In contrast, modest local reactions are observed around the GR clusters. Overall, these results reveal that i.p. injection of GBMs resulted in a modest local tissue reaction without systemic toxicity. This study, performed in swine, provides essential guidance for future biomedical applications of graphene.
Graphene‐Based Pressure Sensor Application in Non‐Invasive Pulse Wave Velocity Continuous Estimation
Authors: Buraioli Irene , Vitale Stefania , Valerio Andrea , Sanginario Alessandro , Leone Dario , Conoci Sabrina , Ciesielski Artur , Milan Alberto , Demarchi Danilo , Samorì Paolo 
Published: October 2024

AbstractMonitoring the cardiovascular health of patients and early diagnosis of heart diseases are highly sought after as they can represent a true cornerstone in tomorrow's healthcare surveillance. Here, an unprecedented non‐invasive device prototype is reported for pulse wave velocity (PWV) measurement based on a piezoelectric graphene pressure sensor. PWV is a critical health indicator that estimates arterial stiffness by measuring the velocity of arterial pulse flow through the circulatory system. The sensor incorporates advanced electronic components and data analysis tools, enabling the measurement of pulse transit time (PTT), that is the time required for the pulse wave to travel between carotid and femoral artery sites. Significantly, the outcomes obtained through the novel method, which involved monitoring 10 patients within clinical environment, show statistical similarity to results obtained using established technology for the PWV estimation such as SphygmoCor. In particular, the mean difference between measurements done with the two techniques resulted in 0.1 m s−1, that is <2%, underscoring the reliability of the novel device. The technology holds big promise for enhancing cardiovascular healthcare delivery: it is wearable, potentially exploitable by a non‐expert user, and it needs to be powered with just 0.2 V, thus it can become compatible even with applications in point‐of‐care settings.
Multi‐Layer LDPE Pouch Robots Enabled by Inkjet‐Printed Masking Layers
Authors: You Yifan , Dai Chen , Goldschmidt Ezequiel , Fearing Ronald S. 
Published: October 2024

AbstractInflatable pouches are attractive as actuators and structural links in soft robots due to their low deflated profile and high deformation ratio. However, current pouch robot fabrication methods have relatively large minimum feature sizes and multi‐layer fabrication challenges, limiting the integration of mechanisms with many independent degrees of freedom (DoF). A new monolithic prototype fabrication method utilizes inkjet printing of a masking ink layer, which prevents film bonding and thus defines inflatable regions. Multi‐layer inflatable pouches of any planar geometry can be created using thermal fusing, with inter‐layer connections and a minimum feature resolution of 0.3 mm. The multi‐layer fabrication process enables the integration of pouches for bending actuation and structure, pneumatic channels, and external port connections. This high level of integration enables the fabrication of pouch robots with many independent DoFs. Specific examples using four layers of 38 micrometer thick Low‐density polyethylene (LDPE) include 1) a 38 mm‐wide 4‐fingered robot hand with 8 independent DoFs which rotates a cube within its palm and 2) a 138 mm‐long planar continuum manipulator with 10 independent DoFs for pick‐and‐place of a cylinder. These example designs demonstrate the capability of ink‐patterned masking to achieve new levels of functionality for thin‐film pouch robots.
Magnetic Nozzle‐Free Embedded 3D (MagNoFE3D) Printing
Authors: Piñan Basualdo Franco N. , Trikalitis Vasileios D. , Visconti Sabrina , Ficuciello Fanny , Goulas Constantinos , Rouwkema Jeroen , Misra Sarthak 
Published: October 2024

AbstractThe functional principle behind extrusion‐based printing is the capability of flowing material through a nozzle on demand, which must solidify upon deposition, a behavior exhibited only by some materials. Embedded printing offers a solution to maintain shape fidelity during the deposition of a wider range of materials. However, the use of a moving nozzle in a support bath can lead to bath disturbance and the spreading of the ink. In this study, a novel embedded printing technique that eliminates the need for a nozzle by employing a magnetic sphere as the plotting moiety is introduced. The externally steered sphere creates a path by locally fluidizing the bath, allowing the simultaneously injected ink to flow into the space behind it. The method is benchmarked using water as an ink, achieving free‐form printing without additional stabilization methods. The creation of solid structures is also demonstrated by printing a photocurable ink that is crosslinked and removed from the bath. Moreover, the plotting magnet can be incorporated into the printed part during the crosslinking, thus giving place to a magnetically responsive structure. This advancement paves the way for innovations in fields such as tissue engineering and microrobotics by enabling the fabrication of intricate and functional designs.
A Three‐Terminal Memristive Artificial Neuron with Tunable Firing Probability
Authors: Lewerenz Mila , Passerini Elias , Weber Luca , Fischer Markus , Jimenez Olalla Nadia , Gisler Raphael , Emboras Alexandros , Luisier Mathieu , Csontos Miklos , Koch Ueli , Leuthold Juerg 
Published: October 2024

AbstractThe human brain facilitates information processing via generating and receiving temporal patterns of short voltage pulses, a.k.a. neural spikes. This approach simultaneously grants low‐power operation as well as a high degree of noise immunity and fault tolerance at a small footprint and simplistic structure of the neurons. To date, the latter two key features are critically missing from the toolbox of artificial spiking neural network hardware, hindering the development of scalable and sustainable artificial intelligence (AI) platforms. Here, a compact, gate‐tunable neuron circuit is demonstrated, and its potential as a functional leaky integrate‐and‐fire (LIF) neuron is explored. It relies on a single nanoscale three‐terminal (3T) memristor device, which has been downscaled by 30% compared to previous work, where the set voltage and, thereby, the spiking probability of the neuron circuit can be widely tuned by the low‐voltage operation of the gate electrode. The influence of the gate voltage on the two‐terminal (2T) current–voltage characteristics is measured, statistically analyzed, and further utilized in a custom‐built LTspice model. The circuit simulations account for the experimentally observed, adjustable set voltage. The presented results demonstrate the merits of 3T memristors as compact, tunable, and versatile artificial neurons for neuromorphic computing applications.
Endoscopic ultrasound‐guided tissue acquisition allows a reliable proliferation assessment of small (≤20 mm) pancreatic neuroendocrine tumors
Authors: Nanno Yoshihide , Toyama Hirochika , Nagai Kazuyuki , Lee Dongha , Uchida Yuichiro , Ishida Jun , Takahara Takeshi , Matsumoto Ippei , Hatano Etsuro , Fukumoto Takumi 
Published: October 2024

AbstractAimEvidence regarding the reliability of endoscopic ultrasound‐guided tissue acquisition (EUS‐TA) for assessing histological proliferation and WHO grading of small (≤20 mm) pancreatic neuroendocrine tumors (PanNETs) is limited.MethodsIn this multicenter retrospective study, we analyzed data from 122 patients with small PanNETs who underwent EUS‐TA followed by surgical resection between 2006 and 2022. We compared the histopathological proliferation assessment and WHO grading between preoperative EUS‐TA and surgical definitive specimens.ResultsAmong the 122 patients with small PanNETs (80% with surgical definitive WHO grade G1 and 20% with G2), EUS‐TA histology identified neuroendocrine tumors in 101 (83%) patients and provided WHO grading in 85 (70%) patients. Histopathological WHO grading for EUS‐TA was concordant with surgical definitive grading in 86% (73/85) of cases, overstaged in 4% (3/85), and understaged in 11% (9/85). Moderate, severe, and fatal adverse events associated with EUS‐TA, as classified by the lexicon, were not reported in this cohort.ConclusionEUS‐TA is a reliable method for assessing histopathological proliferation and WHO grading of small PanNETs. However, grading discordance may occur, and a risk–benefit evaluation on a per‐patient basis is recommended.
Intrinsic role of alkyl side chains in disorder, aggregates, and carrier mobility of nonfullerene acceptors for organic solar cells: A multiscale theoretical study
Authors: Zhou Rongkun , Li Chao , Wen Zihao , Zhang Chen , Shi Yijie , Hou Hao , Chen Xiaoqing , Kang Qian , Zhang Yongzhe , Yan Hui , Yu Han , Zhao Yi , Zheng Zilong , Yan He 
Published: October 2024

AbstractModifications to the alkyl side chains of Y6‐type nonfullerene acceptors (NFAs) continuously break through the organic solar cells (OSCs) efficiency by enhancing electron mobility. However, the role of side chains in molecular aggregation and charge transport across different aggregates remains unclear. By employing a multiscale approach in combination with density functional theory (DFT), molecular dynamics (MD) simulations, and kinetic Monte Carlo (KMC), we addressed the issue of how side chains impact molecular aggregation, energy disorder, and the formation of near‐macroscopic (∼0.3 µm) conductive network, which are critical for boosting electron mobility. Specifically, the side‐chain structure greatly influences the un‐conjugated enveloping effect on backbones within aggregates. The effect diminishes with longer linear side chains and is further minimized by using branched side chains. Though static energy disorder increased, the improved connectivity of the conductive network led to a notable increase in electron mobility (from 2.4 × 10−4 to 3.9 × 10−4 cm2·V−1·s−1). The findings offer insight into controlling molecular aggregation via alkyl side chains, which helps to further unlock the potential of Y6‐type NFAs.
Photochemical synthesis of Ag12Cu7 nanocluster with cuprophilicity‐related long‐lived phosphorescence
Authors: Wang Yu‐Xin , Zhang Fu‐Qiang , Qi Zhikai , Zhao Xingxing , Zhang Nan , Li Hongjin , Li Huan , Zhang Xian‐Ming 
Published: October 2024

AbstractAtomically precise alloyed nanoclusters (NCs) have attracted widespread attention due to synergistic effect but their controllable synthesis remains a challenge. Among them, Ag–Cu alloyed NCs are particularly limited due to significant difference in redox potential, and it is highly desirable to develop controllable and mild synthesis methods. This work proves the feasibility of photochemical synthesis method for Ag12Cu7(4‐tBuPhC≡C)14(Dpppe)3Cl3(SbF6)2 (Ag12Cu7) alloyed NC that exhibits remarkable ligand‐supported cuprophilic interaction. Experimental and time‐dependent UV–Vis spectroscopy first reveals that the formation of Ag12Cu7 is a step‐by‐step process, in which light induces the reduction of Ag+ to Ag19 cluster containing two electrons, then CuCl incorporates into Ag NC to yield the target NC, providing an alternative pathway toward alloyed NCs. Remarkably, Cu···Cu interaction endows Ag12Cu7 with a strong long‐lived red phosphorescence of 30 µs at room temperature, which is superior to the majority of Ag–Cu‐alloyed NCs. Theoretical calculations indicate that the phosphorescence originates from cluster‐centered triplet–excited state modified by cuprophilic interactions, mixed with ligand‐to‐metal charge transfer.
Orthonasal and retronasal olfactory function in patients with chronic rhinosinusitis without nasal polyps undergoing endoscopic sinonasal surgery
Authors: Boscolo‐Rizzo Paolo , Hopkins Claire , Hummel Thomas , Menini Anna , Uderzo Francesco , Provenza Giulia , Spinato Giacomo , Emanuelli Enzo , Tirelli Giancarlo 
Published: October 2024

AbstractBackgroundOlfactory dysfunction (OD) is a key symptom of chronic rhinosinusitis (CRS). Although extensively studied in CRS with nasal polyps (CRSwNP), OD in CRS without nasal polyps (CRSsNP) remains under‐researched. This study aims to assess the prevalence of OD and its evolution in surgically naïve patients with CRSsNP undergoing endoscopic sinus surgery (ESS).MethodsThis prospective study included 97 participants with CRSsNP (mean age, 46.5 years; 70.1% men) and 97 healthy controls (mean age, 46.5 years; 70.1% men). Participants underwent psychophysical evaluations of orthonasal (using the Sniffin’ Sticks test) and retronasal olfaction (using powdered aromas) at enrolment and 6 months post‐ESS.ResultsOut of 97 patients, 81 (83.5%) completed all assessments. At enrolment, 23 (28.4%) CRSsNP patients had OD based on composite threshold, discrimination, identification scores, compared with 7 (8.6%) controls (absolute % difference, 19.8% [95% CI, 8.2–31.4]). Retronasal olfactory function was also significantly worse in CRSsNP patients. Six months post‐ESS, 30 patients (37.0%) experienced a clinically significant improvement in olfactory, whereas nonsignificant changes were observed in retronasal olfactory score, and 3.7% of patients experienced a deterioration of the olfactory function.ConclusionsIn conclusion, although 37% of patients experienced a clinically significant improvement in their sense of smell following ESS, the overall prevalence of OD in this surgically naive population appears relatively low, especially when compared to that observed in patients with CRSwNP. Therefore, ESS may offer some benefits for enhancing orthonasal olfactory function, but the extent of these improvements appears to be limited.
Heightened Reticulospinal Excitability after Severe Corticospinal Damage in Chronic Stroke
Authors: Mooney Ronan A. , Anaya Manuel A. , Stilling Joan M. , Celnik Pablo A. 
Published: October 2024

ObjectiveAfter severe corticospinal tract damage poststroke in humans, some recovery of strength and movement proximally is evident. It is possible that alternate motor pathways, such as the reticulospinal tract, may be upregulated to compensate for the loss of corticospinal tract input. We investigated the extent of reticulospinal tract excitability modulation and its inter‐dependence on the severity of corticospinal tract damage after stroke in humans.MethodsWe used a novel startle conditioned transcranial magnetic stimulation paradigm to elicit ipsilateral motor evoked potentials, an index of reticulospinal tract excitability, in 22 chronic stroke participants with mild to severe corticospinal tract damage and 14 neurotypical age‐matched controls.ResultsWe found that ipsilateral motor evoked potential presence was higher in the paretic arm of people with severe corticospinal tract damage compared to their non‐paretic arm, people with mild corticospinal tract damage, and age‐matched controls. Interestingly, ipsilateral motor evoked potential presence was correlated with motor impairment across the entire stroke cohort, whereby individuals with worse impairment exhibited more frequent ipsilateral motor evoked potentials (ie, higher reticulospinal tract excitability).InterpretationFollowing severe corticospinal tract damage, upregulated reticulospinal tract activity may compensate for a loss of corticospinal tract input, providing some proximal recovery of isolated and within‐synergy movements, but deficits in performing out of synergy movements and finger fractionation remain. Interventions aimed at modulating the reticulospinal tract could be beneficial or detrimental to ameliorating motor impairment depending on the degree of reliance on this pathway for residual motor output. ANN NEUROL 2025;97:163–174
Promoting WLED‐Excited High Temperature Long Afterglow by Orthogonally Anchoring Chromophores into 0D Metal‐Organic Cages
Authors: Wang Zhong‐Hao , Liu Chen‐Hui , Zheng Lin , Sun Hui‐Li , Guan Shao‐Qi , Cao Zhong‐Min , Pan Mei , Su Cheng‐Yong 
Published: October 2024

AbstractAfterglow materials have garnered significant interest due to distinct photophysical characteristics. However, it is still difficult to achieve long afterglow phosphorescence from organic molecules due to aggregation‐caused quenching (ACQ) and energy dissipation. In addition, most materials reported so far have long afterglow emission only at room or even low temperatures, and mainly use UV light as an excitation source. In this work, we report a strategy to achieve high temperature long afterglow emission through the assembly of isolated 0D metal‐organic cages (MOCs). In which, both ACQ and phosphorescence quenching effects are effectively mitigated by altering the stacking mode of organic chromophores through orthogonally anchoring into the edges of cubic MOCs. Furthermore, improvement in molecular rigidity, promotion of spin‐orbit coupling and broadening of the absorption range are achieved through the MOC‐engineering strategy. As a result, we successfully synthesized MOCs that can produce afterglow emission even after excitation by WLEDs at high temperatures (380 K). Moreover, the MOCs are capable of generating afterglow emissions when excited by mobile phone flashlight at room temperature. Given these features, the potential applications of MOCs in the visual identification of explosives, information encryption and multicolor display are explored.
Aerobic Oxidation of Alcohol Over Copper(II)‐Based Metal–Organic Framework: Synthesis, X‐Ray Structure, and Catalytic Study
Authors: Debnath Rakesh , Ghosh Pameli , Koner Subratanath 
Published: October 2024

ABSTRACTA copper‐based one‐dimensional framework compound [Cu2(L1)4(L2)]n (1) [L1 = 3‐(2‐thienyl)acrylic acid, L2 = 4,4′‐bipyridine] has been synthesized by slow diffusion of layers technique and characterized by spectroscopic methods and single‐crystal X‐ray crystallography. X‐ray diffraction analysis reveals that the compound is crystallized in the triclinic crystal system with space group Pī. Two neighboring Cu centers are bridged by four carboxylato groups from four different L1 ligands, leading to the formation of a paddle‐wheel [Cu2(COO−)4] secondary building unit (SBU). The paddle‐wheel units are interconnected by bidentate 4,4′‐bipyridine ligands to form a one‐dimensional infinite chain network. In [Cu2(L1)4(L2)]n (1), Cu(II) ion features a penta‐coordinated environment around it. Notably, [Cu2(L1)4(L2)]n (1) is capable of activating molecular oxygen to efficiently catalyze the oxidation of alcohols under base‐free conditions.
Advances in catalyst design and reaction strategies for carbon‐neutral conversion of bioglycerol to propylene, 1,2‐propanediol, and hydrogen
Authors: El Doukkali M. , Dumeignil F. 
Published: October 2024

AbstractThe inevitable depletion of fossil resources and the resulting anthropogenic climate change require a shift towards renewable feedstocks and eco‐friendly technologies for greener energy, fuel, and chemicals production. This mini‐review highlights our relevant research contributions to advance the production of carbon‐neutral propylene, 1,2‐propanediol and biohydrogen through thermo‐chemical conversion of biomass‐derived glycerol, using various heterogeneous catalysts. These achievements, recently recognized by the “ACI/NBB Glycerine Innovation Award,” are organized into shared sections: (i) economic and environmental benefits of utilizing surplus bioglycerol, as feedstock, (ii) strategies to improve the properties of transition metals‐based catalysts (e.g., Pt, Pd, Ni, Cu or Mo supported on γ‐Al2O3 or SiO2) for glycerol conversion via: steam reforming, aqueous‐phase reforming, hydrogenolysis, and hydrodeoxygenation reactions, (iii) discussion on the catalytic roles of metallic, acidic and/or redox sites, and keys factors affecting catalyst stability and selectivity in these reactions operated under H2O‐rich conditions, and (iv) assessment of reaction configurations and operating conditions for improved glycerol conversion into the target product, H2 utilization efficiency and CO2 emissions. The insights aim to guide the continuous improvement of bioglycerol upgrading processes.