bluuebunny/crossref_metadata_2025_split huggingface dataset:
2D Ferromagnetic M3GeTe2 (M = Ni/Fe) for Boosting Intermediates Adsorption toward Faster Water Oxidation
Authors: Bo Guyue , Li Peng , Fan Yameng , Zheng Xiaobo , Zhao Mengting , Zhu Qiang , Fu Yang , Li Yitong , Pang Wei Kong , Lai Wei Hong , Johannessen Bernt , Thomsen Lars , Cowie Bruce , Ma Tianyi , Wang Cheng , Yeoh Guan Heng , Du Yi , Dou Shi Xue , Xu Xun 
Published: March 2024

AbstractIn this work, 2D ferromagnetic M3GeTe2 (MGT, M = Ni/Fe) nanosheets with rich atomic Te vacancies (2D‐MGTv) are demonstrated as efficient OER electrocatalyst via a general mechanical exfoliation strategy. X‐ray absorption spectra (XAS) and scanning transmission electron microscope (STEM) results validate the dominant presence of metal‐O moieties and rich Te vacancies, respectively. The formed Te vacancies are active for the adsorption of OH* and O* species while the metal‐O moieties promote the O* and OOH* adsorption, contributing synergistically to the faster oxygen evolution kinetics. Consequently, 2D‐Ni3GeTe2v exhibits superior OER activity with only 370 mV overpotential to reach the current density of 100 mA cm−2 and turnover frequency (TOF) value of 101.6 s−1 at the overpotential of 200 mV in alkaline media. Furthermore, a 2D‐Ni3GeTe2v‐based anion‐exchange membrane (AEM) water electrolysis cell (1 cm2) delivers a current density of 1.02 and 1.32 A cm−2 at the voltage of 3 V feeding with 0.1 and 1 m KOH solution, respectively. The demonstrated metal‐O coordination with abundant atomic vacancies for ferromagnetic M3GeTe2 and the easily extended preparation strategy would enlighten the rational design and fabrication of other ferromagnetic materials for wider electrocatalytic applications.
Asymmetrical Interactions between Ni Single Atomic Sites and Ni Clusters in a 3D Porous Organic Framework for Enhanced CO2 Photoreduction
Authors: Yan Fang‐Qin , Dong Xiao‐Yu , Wang Yi‐Man , Wang Qian‐You , Wang Shan , Zang Shuang‐Quan 
Published: March 2024

Abstract3D porous organic frameworks, which possess the advantages of high surface area and abundant exposed active sites, are considered ideal platforms to accommodate single atoms (SAs) and metal nanoclusters (NCs) in high‐performance catalysts; however, very little research has been conducted in this field. In the present work, a 3D porous organic framework containing Ni1 SAs and Nin NCs is prepared through the metal‐assisted one‐pot polycondensation of tetraaldehyde and hexaaminotriptycene. The single metal sites and metal clusters confined in the 3D space created a favorable micro‐environment that facilitated the activation of chemically inert CO2 molecules, thus promoting the overall photoconversion efficiency and selectivity of CO2 reduction. The 3D‐NiSAs/NiNCs‐POPs, as a CO2 photoreduction catalyst, demonstrated an exceptional CO production rate of 6.24 mmol g−1 h−1, high selectivity of 98%, and excellent stability. The theoretical calculations uncovered that asymmetrical interaction between Ni1 SAs and Nin NCs not only favored the bending of CO2 molecules and reducing the CO2 reduction energy, but also regulated the electronic structure of the catalyst leading to the optimal binding strength of intermediates.
Boosting Energy Deprivation by Synchronous Interventions of Glycolysis and Oxidative Phosphorylation for Bioenergetic Therapy Synergetic with Chemodynamic/Photothermal Therapy
Authors: Wei Xiangjun , Han Renlu , Gao Yun , Song Pengxin , Guo Zhen , Hou Yafei , Yu Jiancheng , Tang Keqi 
Published: March 2024

AbstractBioenergetic therapy is emerging as a promising therapeutic approach. However, its therapeutic effectiveness is restricted by metabolic plasticity, as tumor cells switch metabolic phenotypes between glycolysis and oxidative phosphorylation (OXPHOS) to compensate for energy. Herein, Metformin (MET) and BAY‐876 (BAY) co‐loaded CuFe2O4 (CF) nanoplatform (CFMB) is developed to boost energy deprivation by synchronous interventions of glycolysis and OXPHOS for bioenergetic therapy synergetic with chemodynamic/photothermal therapy (CDT/PTT). The MET can simultaneously restrain glycolysis and OXPHOS by inhibiting hexokinase 2 (HK2) activity and damaging mitochondrial function to deprive energy, respectively. Besides, BAY blocks glucose uptake by inhibiting glucose transporter 1 (GLUT1) expression, further potentiating the glycolysis repression and thus achieving much more depletion of tumorigenic energy sources. Interestingly, the upregulated antioxidant glutathione (GSH) in cancer cells triggers CFMB degradation to release Cu+/Fe2+ catalyzing tumor‐overexpressed H2O2 to hydroxyl radical (∙OH), both impairing OXPHOS and achieving GSH‐depletion amplified CDT. Furthermore, upon near‐infrared (NIR) light irradiation, CFMB has a photothermal conversion capacity to kill cancer cells for PTT and improve ∙OH production for enhanced CDT. In vivo experiments have manifested that CFMB remarkably suppressed tumor growth in mice without systemic toxicity. This study provides a new therapeutic modality paradigm to boost bioenergetic‐related therapies.
Phonon‐Bottleneck Enhanced Exciton Emission in 2D Perovskites
Authors: Thompson Joshua J. P. , Dyksik Mateusz , Peksa Paulina , Posmyk Katarzyna , Joki Ambjörn , Perea‐Causin Raul , Erhart Paul , Baranowski Michał , Loi Maria Antonietta , Plochocka Paulina , Malic Ermin 
Published: March 2024

AbstractLayered halide perovskites exhibit remarkable optoelectronic properties and technological promise, driven by strongly bound excitons. The interplay of spin‐orbit and exchange coupling creates a rich excitonic landscape, determining their optical signatures and exciton dynamics. Despite the dark excitonic ground state, surprisingly efficient emission from higher‐energy bright states has puzzled the scientific community, sparking debates on relaxation mechanisms. Combining low‐temperature magneto‐optical measurements with sophisticated many‐particle theory, the origin of the bright exciton emission in perovskites is elucidated by tracking the thermalization of dark and bright excitons under a magnetic field. The unexpectedly high emission is clearly attributed to a pronounced phonon‐bottleneck effect, considerably slowing down the relaxation toward the energetically lowest dark states. It is demonstrated that this bottleneck can be tuned by manipulating the bright‐dark energy splitting and optical phonon energies, offering valuable insights and strategies for controlling exciton emission in layered perovskite materials that is crucial for optoelectronics applications.
Impact of malnutrition and nutritional support after gastrectomy in patients with gastric cancer
Authors: Kang Min Kyu , Lee Hyuk‐Joon 
Published: March 2024

AbstractMalnutrition, characterized by altered body composition and impaired function, is particularly prevalent among gastric cancer patients, affecting up to 60% of them. Malnutrition in these patients can manifest both before and after surgery, due to factors such as gastric outlet obstruction, cancer cachexia, and anatomical changes. Notably, total gastrectomy (TG) presents the most significant nutritional challenges. However, function‐preserving gastrectomy, such as pylorus‐preserving gastrectomy (PPG) and proximal gastrectomy (PG), have shown promise in improving nutritional outcomes. Effective nutritional risk screening and assessment are vital for identifying patients at risk. Nutritional support not only improves nutritional parameters but also reduces complications, enhances quality of life (QoL) and survival rates. Those unable to maintain more than 50% of the recommended intake for over 7 days are recommended for nutritional support. Common methods of nutritional support include oral nutrition supplements (ONS), enteral nutrition (EN), or parenteral nutrition (PN) depending on the patient's status. Effect of perioperative nutritional support remains controversial. Preoperative interventions including ONS and PN have shown mixed results, with selective benefits in patients with sarcopenia or hypoalbuminaemia, while impact of EN in gastric outlet obstruction patients have been positive. In contrast postoperative support appears to be consistent. Tube feeding after TG has shown improvements, and ONS have been effective in reducing weight loss and improving nutritional biomarkers. PN was also associated with benefits such as weight maintenance and QoL. This review explores the mechanisms, assessment, and clinical impact of malnutrition, emphasizing the importance of nutritional support in gastric cancer patients undergoing gastrectomy.
Short‐acting opioid prescriptions and Workers' Compensation using the National Ambulatory Medical Care Survey
Authors: Thompson Hannah M. , Govindarajulu Usha , Doucette John , Nabeel Ismail 
Published: March 2024

AbstractBackgroundShort‐acting opioids have been utilized for pain management with little known about their use in patients on Workers' Compensation (WC) insurance. Our goal was to investigate this association in the ambulatory care setting.MethodsUsing the National Ambulatory Medical Care Survey, visits from patients aged 18–64 during the years 2010 until 2018 were evaluated (excluding 2017 due to data availability). Demographic and co‐morbidity data from each visit was obtained along with the visit year. The first short‐acting opioid medication prescribed in the database was considered. Survey‐weighted frequencies were evaluated. Logistic regression estimated the crude and adjusted odds ratios (OR) with 95% confidence intervals for the use of short‐acting opioid prescription.ResultsThere were 155,947 included visits with 62.5% for female patients. Most patients were White with 11.7% identifying as Black, and 6% identifying as another race. Over 13% of the sample was of Hispanic descent. WC was the identified insurance type in 1.6% of the sample population. Of these patients, 25.6% were prescribed a short‐acting opioid, compared with 10.1% of those with another identified insurance. On multivariable regression, Black patients had increased odds of being prescribed a short‐acting opioid compared to white patients (OR: 1.22, 95% CI: 1.11–1.34). Those on WC had 1.7‐fold higher odds of being prescribed short‐acting opioids (95% CI: 1.46–2.06).ConclusionCertain patient characteristics, including having WC insurance, increased the odds of a short‐acting opioid prescription. Further work is needed to identify prescribing patterns in specific high‐risk occupational groups, as well as to elicit potential associated health outcomes.
Effects of the active amyloid beta immunotherapy CAD106 on PET measurements of amyloid plaque deposition in cognitively unimpaired APOE ε4 homozygotes
Authors: Riviere Marie‐Emmanuelle , Langbaum Jessica B. , Turner R. Scott , Rinne Juha O. , Sui Yihan , Cazorla Pilar , Ricart Javier , Meneses Kathleen , Caputo Angelika , Tariot Pierre N. , Reiman Eric M. , Graf Ana 
Published: March 2024

AbstractINTRODUCTIONAlzheimer's Prevention Initiative Generation Study 1 evaluated amyloid beta (Aβ) active immunotherapy (vaccine) CAD106 and BACE‐1 inhibitor umibecestat in cognitively unimpaired 60‐ to 75‐year‐old participants at genetic risk for Alzheimer's disease (AD). The study was reduced in size and terminated early. Results from the CAD106 cohort are presented.METHODSSixty‐five apolipoprotein E ε4 homozygotes with/without amyloid deposition received intramuscular CAD106 450 μg (n = 42) or placebo (n = 23) at baseline; Weeks 1, 7, 13; and quarterly; 51 of them had follow‐up Aβ positron emission tomography (PET) scans at 18 to 24 months.RESULTSCAD106 induced measurable serum Aβ immunoglobulin G titers in 41/42 participants, slower rates of Aβ plaque accumulation (mean [standard deviation] annualized change from baseline in amyloid PET Centiloid: −0.91[5.65] for CAD106 versus 8.36 [6.68] for placebo; P < 0.001), and three amyloid‐related imaging abnormality cases (one symptomatic).DISCUSSIONDespite early termination, these findings support the potential value of conducting larger prevention trials of Aβ active immunotherapies in individuals at risk for AD.Highlights
This was the first amyloid‐lowering prevention trial in persons at genetic risk of late‐onset Alzheimer's disease (AD).
Active immunotherapy targeting amyloid (CAD106) was tested in this prevention trial.
CAD106 significantly slowed down amyloid plaque deposition in apolipoprotein E homozygotes.
CAD106 was generally safe and well tolerated, with only three amyloid‐related imaging abnormality cases (one symptomatic).
Such an approach deserves further evaluation in larger AD prevention trials.
Carrier Protein Interaction with Competing Adenylation and Epimerization Domains in a Nonribosomal Peptide Synthetase Analyzed by FRET
Authors: Feldberg Anna‐Lena , Mayerthaler Florian , Rüschenbaum Jennifer , Kröger Jonas , Mootz Henning D. 
Published: March 2024

AbstractIn multi‐domain nonribosomal peptide synthetases (NRPSs) the order of domains and their catalytic specificities dictate the structure of the peptide product. Peptidyl‐carrier proteins (PCPs) bind activated amino acids and channel elongating peptidyl intermediates along the protein template. To this end, fine‐tuned interactions with the catalytic domains and large‐scale PCP translocations are necessary. Despite crystal structure snapshots of several PCP‐domain interactions, the conformational dynamics under catalytic conditions in solution remain poorly understood. We report a FRET reporter of gramicidin S synthetase 1 (GrsA; with A‐PCP‐E domains) to study for the first time the interaction between PCP and adenylation (A) domain in the presence of an epimerization (E) domain, a competing downstream partner for the PCP. Bulk FRET measurements showed that upon PCP aminoacylation a conformational shift towards PCP binding to the A domain occurs, indicating the E domain acts on its PCP substrate out of a disfavored conformational equilibrium. Furthermore, the A domain was found to preferably bind the D‐Phe‐S‐Ppant‐PCP stereoisomer, suggesting it helps in establishing the stereoisomeric mixture in favor of the D‐aminoacyl moiety. These observations surprisingly show that the conformational logic can deviate from the order of domains and thus reveal new principles in the multi‐domain interplay of NRPSs.
The Transfer Dehydrogenation Method Enables a Family of High Crystalline Benzimidazole‐linked Cu (II)‐phthalocyanine‐based Covalent Organic Frameworks Films
Authors: Zhang Qingsong , Zhu Zhiheng , Liu Liping , Huang Haojie , Chen Xianjie , Bian Yangshuang , Shao Mingchao , Wei Xiaofang , Wang Chengyu , Wang Dong , Dong Jichen , Guo Yunlong , Zhu Yongfa , Liu Yunqi 
Published: March 2024

AbstractHeterocycle‐linked phthalocyanine‐based COFs with close‐packed π–π conjugated structures are a kind of material with intrinsic electrical conductivity, and they are considered to be candidates for photoelectrical devices. Previous studies have revealed their applications for energy storage, gas sensors, and field‐effect transistors. However, their potential application in photodetector is still not fully studied. The main difficulty is preparing high‐quality films. In our study, we found that our newly designed benzimidazole‐linked Cu (II)‐phthalocyanine‐based COFs (BICuPc‐COFs) film can hardly formed with a regular aerobic oxidation method. Therefore, we developed a transfer dehydrogenation method with N‐benzylideneaniline (BA) as a mild reagent. With this in hand, we successfully prepared a family of high crystalline BICuPc‐COFs powders and films. Furthermore, both of these new BICuPc‐COFs films showed high electrical conductivity (0.022–0.218 S/m), higher than most of the reported COFs materials. Due to the broad absorption and high conductivity of BICuPc‐COFs, synaptic devices with small source‐drain voltage (VDS=1 V) were fabricated with response light from visible to near‐infrared. Based on these findings, we expect this study will provide a new perspective for the application of conducting heterocycle‐linked COFs in synaptic devices.
Rocking‐Chair Aqueous Fluoride‐Ion Batteries Enabled by Hydrogen Bonding Competition
Authors: Wang Huijian , Lei Chengjun , Liu Tingting , Xu Chen , He Xin , Liang Xiao 
Published: March 2024

AbstractAqueous fluoride ion batteries (FIBs) have garnered attention for their high theoretical energy density, yet they are challenged by sluggish fluorination kinetics, active material dissolution, and electrolyte instability. Here, we present a room temperature rocking‐chair aqueous FIBs featuring KOAc‐KF binary salt electrolytes, enabling concurrent fluorination and defluorination reactions at both cathode and anode electrodes. Experimental and theoretical results reveal that acetate ions in the electrolyte compete with fluoride ions in hydrogen bonding formation, weakening the excessively strong solvation between H2O and F− ions. This results in the suppression of detrimental HF formation and a reduced desolvation energy of F− ions, enhancing the electrochemical reaction kinetics. The bismuth‐based cathode exhibits direct conversion in the optimized electrolyte, effectively suppressing the detrimental disproportionation reactions from Bi2+ intermediates. Additionally, zinc anode undergoes a typical fluorination process, forming solid KZnF3 as the electrode product, minimizing the risks of hydrogen evolution. The proposed aqueous FIBs with the optimized electrolyte demonstrate high discharge capacity, long‐term cycling stability and excellent rate capabilities.
Interfacial Engineering for Oriented Crystal Growth toward Dendrite‐Free Zn Anode for Aqueous Zinc Metal Battery
Authors: Zhou Xunzhu , Wen Bo , Cai Yichao , Chen Xiaomin , Li Lin , Zhao Qing , Chou Shu‐Lei , Li Fujun 
Published: March 2024

AbstractZn deposition with a surface‐preferred (002) crystal plane has attracted extensive attention due to its inhibited dendrite growth and side reactions. However, the nucleation and growth of the Zn(002) crystal plane are closely related to the interfacial properties. Herein, oriented growth of Zn(002) crystal plane is realized on Ag‐modified surface that is directly visualized by in situ atomic force microscopy. A solid solution HCP‐Zn (~1.10 at. % solubility of Ag, 30 °C) is formed on the Ag coated Zn foil (Zn@Ag) and possesses the same crystal structure as Zn to reduce its nucleation barrier caused by their lattice mismatch. It merits oriented Zn deposition and corrosion‐resistant surface, and presents long cycling stability in symmetric cells and full cells coupled with V2O5 cathode. This work provides insights into interfacial regulation of Zn anodes for high‐performance aqueous zinc metal batteries.
Copper Nanodrugs by Atom Transfer Radical Polymerization
Authors: Chen Peng , Song Ziyan , Yao Xuxia , Wang Weibin , Teng Lisong , Matyjaszewski Krzysztof , Zhu Weipu 
Published: March 2024

AbstractIn this study, some copper catalysts used for atom transfer radical polymerization (ATRP) were explored as efficient anti‐tumor agents. The aqueous solution of copper‐containing nanoparticles with uniform spheric morphology was in situ prepared through a copper‐catalyzed activator generated by electron transfer (AGET) ATRP in water. Nanoparticles were then directly injected into tumor‐bearing mice for antitumor chemotherapy. The copper nanodrugs had prolonged blood circulation time and enhanced accumulation at tumor sites, thus showing potent antitumor activity. This work provides a novel strategy for precise and large‐scale preparation of copper nanodrugs with high antitumor activity.
Selective Peptide Cysteine Manipulation on Demand and Difficult Protein Chemical Synthesis Enabled by Controllable Acidolysis of N,S‐Benzylidene Thioacetals
Authors: Wu Hongxiang , Sun Zhenquan , Li Xuechen 
Published: March 2024

AbstractAlthough solid‐phase peptide synthesis combining with chemical ligation provides a way to build up customized polypeptides in general, many targets are still presenting challenges for the conventional synthetic process, such as hydrophobic proteins. New methods and strategies are still required to overcome these obstacles. In this study, kinetic studies of Cys/Pen ligation and its acidolysis were performed, from which the fast acidolysis of substituted N,S‐benzylidene thioacetals (NBTs) was discovered. The study demonstrates the potential of NBTs as a promising Cys switchable protection, facilitating the chemical synthesis of peptides and proteins by efficiently disrupting peptide aggregation. The compatibility of NBTs with other commonly adopted Cys protecting groups and their applications in sequential disulfide bond formation were also investigated. The first chemical synthesis of the native human programmed death ligand 1 immunoglobulin V‐like (PD‐L1 IgV) domain was achieved using the NBT strategy, showcasing its potential in difficult protein synthesis.
Abiotic Methane Production Driven by Ubiquitous Non‐Fenton‐Type Reactive Oxygen Species
Authors: Ye Jie , Hu Andong , Gao Chao , Li Fengqi , Li Lei , Guo Yulin , Ren Guoping , Li Bing , Rensing Christopher , Nealson Kenneth H. , Zhou Shungui , Xiong Yujie 
Published: March 2024

AbstractAbiotic CH4 production driven by Fenton‐type reactive oxygen species (ROS) has been confirmed to be an indispensable component of the atmospheric CH4 budget. While the chemical reactions independent of Fenton chemistry to ROS are ubiquitous in nature, it remains unknown whether the produced ROS can drive abiotic CH4 production. Here, we first demonstrated the abiotic CH4 production at the soil‐water interface under illumination. Leveraging this finding, polymeric carbon nitrides (CNx) as a typical analogue of natural geobattery material and dimethyl sulfoxide (DMSO) as a natural methyl donor were used to unravel the underlying mechanisms. We revealed that the ROS, photocatalytically produced by CNx, can oxidize DMSO into CH4 with a high selectivity of 91.5 %. Such an abiotic CH4 production process was further expanded to various non‐Fenton‐type reaction systems, such as electrocatalysis, pyrocatalysis and sonocatalysis. This work provides insights into the geochemical cycle of abiotic CH4, and offers a new route to CH4 production via integrated energy development.
Catalyst‐Free α‐Acetyl Cinnamate/Acetoacetate Exchange to Enable High Creep‐Resistant Vitrimers
Authors: Feng Hongzhi , Wang Sheng , Lim Jason Y. C. , Li Bofan , Rusli Wendy , Liu Feng , Hadjichristidis Nikos , Li Zibiao , Zhu Jin 
Published: March 2024

AbstractVitrimers represent an emerging class of polymeric materials that combine the desirable characteristics of both thermoplastics and thermosets achieved through the design of dynamic covalent bonds within the polymer networks. However, these materials are prone to creep due to the inherent instability of dynamic covalent bonds. Consequently, there are pressing demands for the development of robust and stable dynamic covalent chemistries. Here, we report a catalyst‐free α‐acetyl cinnamate/acetoacetate (α‐AC/A) exchange reaction to develop vitrimers with remarkable creep resistance. Small‐molecule model studies revealed that the α‐AC/A exchange occurred at temperatures above 140 °C in bulk, whereas at 120 °C, this reaction was absent. For demonstration in the case of polymers, copolymers derived from common vinyl monomers were crosslinked with terephthalaldehyde to produce α‐AC/A vitrimers with tunable thermal and mechanical performance. All resulting α‐AC/A vitrimers exhibited high stability, especially in terms of creep resistance at 120 °C, while retaining commendable reprocessability when subjected to high temperatures. This work showcases the α‐AC/A exchange reaction as a novel and robust dynamic covalent chemistry capable of imparting both reprocessability and high stability to cross‐linked networks.