bluuebunny/crossref_metadata_2025_split huggingface dataset:
Facet‐Junction Induced Strong Metal Support Interaction for Enhanced Alkaline Hydrogen Evolution Reaction
Authors: Shen Wenqian , Fu Qiang , Tsang Chi Shing , Wong Lok Wing , Zheng Xiaodong , Zhao Jiong , Ly Thuc Hue 
Published: May 2024

AbstractStrong metal‐support interaction (SMSI) plays a critical role in enhancing the catalytic performance of electrocatalysts. Currently, effective approaches to enhance the SMSI effect in supported electrocatalysts still need to be developed, and a comprehensive atomic‐level understanding of the underlying reaction mechanisms remains unclear. In this study, a novel facet‐junction strategy is proposed to enhance the SMSI between the loaded Ru atoms and the Co3O4 support. By modulating the ratio of exposed facet for (111)/(100) crystal plane in Co3O4, the hydrogen evolution reaction (HER) performance can be dramatically enhanced by 560% and can achieve a Pt‐like HER activity with the overpotential of 45 mV. Detailed analysis with atomic‐resolution integrated differential phase contrast (iDPC)‐scanning transmission electron microscopy (STEM), atomic‐resolution high angle annular dark field (HADDF)‐STEM, and electron energy loss spectroscopy (EELS) further proved that with proper (111)/(100) crystal plane ratio, the intensified charge distribution near the facet‐junction region would modify the electronic structure around the active sites. This work provides new insights to enhance the SMSI and will contribute to the rational design of highly efficient electrocatalysts for water splitting.
Preparation of NIR‐II Polymer Nanoprobe Through Twisted Intramolecular Charge Transfer and Förster Resonance Energy Transfer of NIR‐I Dye
Authors: Xia Bin , Ren Feng , Ma Xiaopeng , Yang Zheng‐Chuan , Jiang Zhi‐Lin , Fang Wei‐Wei , Wang Ning‐Wei , Hu Jin‐Long , Zhu Wei‐Duo , He Tao , Li Qing , Cao Bao‐Qiang , Li Zhen 
Published: May 2024

AbstractNear‐infrared‐II (NIR‐II) fluorescence imaging is pivotal in biomedical research. Organic probes exhibit high potential in clinical translation, due to advantages such as precise structure design, low toxicity, and post‐modifications convenience. In related preparation, enhancement of NIR‐II tail emission from NIR‐I dyes is an efficient method. In particular, the promotion of twisted intramolecular charge transfer (TICT) of relevant NIR‐I dyes is a convenient protocol. However, present TICT‐type probes still show disadvantages in relatively low emission, large particle sizes, or limited choice of NIR‐I dyes, etc. Herein, the synthesis of stable small‐sized polymer NIR‐II fluoroprobes (e.g., 7.2 nm), integrating TICT and Förster resonance energy transfer process to synergistically enhance the NIR‐II emission is reported. Strong enhanced emissions can be obtained from various NIR‐I dyes and lanthanide elements (e.g., twelvefold at 1250 nm from Nd‐DTPA/IR‐808 sample). The fluorophore provides high‐resolution angiography, with high‐contrast imaging on middle cerebral artery occlusion model mice for distinguishing occlusion. The fluorophore can be rapidly excreted from the kidney (urine ≈65% within 4 h) in normal mice and exhibits long‐term renal retention on acute kidney injury mice, showing potential applications in the prognosis of kidney diseases. This development provides an effective strategy to design and synthesize effective NIR‐II fluoroprobes.
An Engineered Nanoplatform with Tropism Toward Irradiated Glioblastoma Augments Its Radioimmunotherapy Efficacy
Authors: Wang Zheng , Chen Fangman , Cao Yi , Zhang Fan , Sun Lina , Yang Chao , Xie Xiaochun , Wu Ziping , Sun Madi , Ma Fanshu , Shao Dan , Leong Kam W. , Pei Renjun 
Published: May 2024

AbstractCombining radiotherapy with immune checkpoint blockade therapy offers a promising approach to treat glioblastoma multiforme (GBM), yet challenges such as limited effectiveness and immune‐related adverse events (irAEs) persist. These issues are largely due to the failure in targeting immunomodulators directly to the tumor microenvironment. To address this, a biomimetic nanoplatform that combines a genetically modified mesenchymal stem cell (MSC) membrane with a bioactive nanoparticle core for chemokine‐directed radioimmunotherapy of GBM is developed. The CC chemokine receptor 2 (CCR2)‐overexpressing MSC membrane acts as a tactical tentacle to achieve radiation‐induced tropism toward the abundant chemokine (CC motif) ligand 2 (CCL2) in irradiated gliomas. The nanoparticle core, comprising diselenide‐bridged mesoporous silica nanoparticles (MSNs) and PD‐L1 antibodies (αPD‐L1), enables X‐ray‐responsive drug release and radiosensitization. In two murine models with orthotopic GBM tumors, this nanoplatform reinvigorated immunogenic cell death, and augmented the efficacy and specificity of GBM radioimmunotherapy, with reduced occurrence of irAEs. This study suggests a promising radiation‐induced tropism strategy for targeted drug delivery, and presents a potent nanoplatform that enhances the efficacy and safety of radio‐immunotherapy.
Implication Logic Circuit Based on a Graphene Oxide Complementary Resistive Switching Device
Authors: Wang Lu , Zuo Ze , Zhang Xiafan , Wen Dianzhong 
Published: May 2024

AbstractThe logic circuit is the main component of an integrated circuit chip that dictates the operation and performance of the chip. The logic circuit based on a memristor can improve the integration and operation speed of the existing integrated circuit and reduce the chip size and the number of devices used by a single logic circuit. However, most of the research on logic circuits based on memristors has focused only on simulations, and research on the realization of logic circuits by hardware using actual memristors is limited. In this paper, a memristor based on graphene oxide with stable complementary resistive switching characteristics is fabricated, a logic circuit is built by using this device, and the logic functions of “IMP,” “AND,” and “NOR” are successfully realized. The complementary resistive switching device can alleviate the severe power loss caused by the memory separation of the von Neumann architecture. Moreover, its unique structure enables it to realize material logic independently without the use of multiple memristors and resistors, providing a new scheme for the physical realization of logic circuits. It also opens up a new path for integrated chips to break through von Neumann architecture.
Pd‐Catalyzed [3+6+3+6] Macrocyclizations of Aryl α‐Diazo‐β‐Ketoesters
Authors: Zhong Zhuang , de Aguirre Adiran , Besnard Céline , Poblador‐Bahamonde Amalia I. , Lacour Jérôme 
Published: May 2024

AbstractThanks to Pd(II)‐catalysis, an efficient synthesis of unsaturated macrocycles is achieved by [3+6+3+6] condensation of cyclic ethers with aryl α‐diazo‐β‐ketoesters. The presence of the electron‐rich aryl ester moieties forbids the use of dirhodium complexes as these diazo decomposition catalysts provoke unforeseen intermolecular Csp2−H insertion reactions that derail the targeted reactivity. However, with Pd(acac)2, using high concentration conditions (1 M), a variety of 18‐membered macrocycles (16 examples) is afforded with both aryl and alkyl diazo reagents. Catalyst selection for either electrophilic aromatic substitution (Rh) or ylide (Pd) pathways are explained by computational approaches.
Synthesis of Phthalazino[2,3‐a]cinnoline‐6,8,13(5H)‐triones via Ir(III)‐Catalyzed Dehydrogenative C−H/N−H Functionalization of N‐Aryl Phthalazinones
Authors: Zhang Chao , Zhang Ling‐Xi , Dong Lin 
Published: May 2024

AbstractAn Iridium(III)‐catalyzed C−H cyclization of N‐arylphthalazinones with α‐diazotized Meldrum's acid afforded tetracyclic phthalazine derivatives with a carbonyl group in 98% yield in only 30 min. The initial formation of tetracyclic phthalazine derivatives also provided access to a powerful building block. The utility of this method is emphasized by the synthetic transformation into a series of potentially bioactive derivatives.
Modeling self‐diffusion coefficients of ionic liquids using ePC‐SAFT and FVT combined with Einstein relation
Authors: Zuo Zhida , Lu Xiaohua , Ji Xiaoyan 
Published: May 2024

AbstractThe electrolyte perturbed‐chain statistical associating fluids theory (ePC‐SAFT) coupled with free volume theory (FVT) was combined with Einstein relation, that is, ePC‐SAFT‐FVT‐E, to describe self‐diffusion coefficients (SDCs) of ionic liquids (ILs). In modeling, ePC‐SAFT was used to calculate density, while FVT parameters, determined from viscosity data, were utilized to calculate the summation of ionic SDCs through the Einstein relation with one parameter. Two strategies were employed to determine this parameter: fitting experimental data for each IL or estimating a universal parameter from van der Waals volume. Comparative analysis reveals good agreement with experimental data, with average absolute relative deviations (ARDs) of 8.14% (strategy 1) and 10.29% (strategy 2). Subsequently, cationic and anionic SDCs were reliably determined from the summation of ionic SDCs, with average ARDs of 10.80% and 10.21%, respectively. This study indicates the ePC‐SAFT‐FVT‐E model, employing viscosity‐derived parameters and three universal parameters, reliably predicts SDCs of ILs in wide temperature and pressure ranges.
Unburdening care: Exploring modes of care through post‐productivist thought and Australian parliamentary inquiry representations
Authors: Khan Chabel 
Published: May 2024

AbstractResearch on care increasingly emphasises the “care‐less” or “uncaring” nature of state‐coordinated interventions imposed on marginalised communities. However, these perspectives tend to eliminate discussions about modes of care (Fox, Critical Social Policy, 15, 1995, 107) or the ways in which care is differentially experienced and performed. This paper argues for scholars to think multimodally about care, proposing a typology of four different modes of care: care‐as‐gift, ‐burden, ‐control and ‐cure. The paper makes a case for locating these modes of care within a post‐capitalist political horizon to respond to the demand to “unburden care.” That is, the political demand to provide the economic and social conditions that best enable caregiving and reduce gendered pressures on caregivers. The paper develops these arguments through the post‐productivist thought of Kathi Weeks (2011, The problem with work: feminism, marxism, antiwork politics, and postwork imaginaries. Durham, NC and London: Duke University Press) and a critical discursive examination of care representations made by submitters to two parliamentary inquiries into the Australian “pre‐employment” programme ParentsNext—a labour market activation programme that targets single‐parent caregivers “at risk of welfare dependency.” The paper contributes a critical and multimodal approach to better conceptualise competing framings of care's value and the ways in which the state can (un)burden caregiving.
Assessment of neurovascular uncoupling: APOE status is a key driver of early metabolic and vascular dysfunction
Authors: Onos Kristen D. , Lin Peter B. , Pandey Ravi S. , Persohn Scott A. , Burton Charles P. , Miner Ethan W. , Eldridge Kierra , Kanyinda Jonathan Nyandu , Foley Kate E. , Carter Gregory W. , Howell Gareth R. , Territo Paul R. 
Published: May 2024

AbstractBACKGROUNDAlzheimer's disease (AD) is the most common cause of dementia worldwide, with apolipoprotein Eε4 (APOEε4) being the strongest genetic risk factor. Current clinical diagnostic imaging focuses on amyloid and tau; however, new methods are needed for earlier detection.METHODSPET imaging was used to assess metabolism‐perfusion in both sexes of aging C57BL/6J, and hAPOE mice, and were verified by transcriptomics, and immunopathology.RESULTSAll hAPOE strains showed AD phenotype progression by 8 months, with females exhibiting the regional changes, which correlated with GO‐term enrichments for glucose metabolism, perfusion, and immunity. Uncoupling analysis revealed APOEε4/ε4 exhibited significant Type‐1 uncoupling (↓ glucose uptake, ↑ perfusion) at 8 and 12 months, while APOEε3/ε4 demonstrated Type‐2 uncoupling (↑ glucose uptake, ↓ perfusion), while immunopathology confirmed cell specific contributions.DISCUSSIONThis work highlights APOEε4 status in AD progression manifests as neurovascular uncoupling driven by immunological activation, and may serve as an early diagnostic biomarker.Highlights
We developed a novel analytical method to analyze PET imaging of 18F‐FDG and 64Cu‐PTSM data in both sexes of aging C57BL/6J, and hAPOEε3/ε3, hAPOEε4/ε4, and hAPOEε3/ε4 mice to assess metabolism‐perfusion profiles termed neurovascular uncoupling.
This analysis revealed APOEε4/ε4 exhibited significant Type‐1 uncoupling (decreased glucose uptake, increased perfusion) at 8 and 12 months, while APOEε3/ε4 demonstrated significant Type‐2 uncoupling (increased glucose uptake, decreased perfusion) by 8 months which aligns with immunopathology and transcriptomic signatures.
This work highlights that there may be different mechanisms underlying age related changes in APOEε4/ε4 compared with APOEε3/ε4. We predict that these changes may be driven by immunological activation and response, and may serve as an early diagnostic biomarker.
Synthetic Sialosides Terminated with 8‐N‐Substituted Sialic Acid as Selective Substrates for Sialidases from Bacteria and Influenza Viruses
Authors: Mishra Bijoyananda , Yuan Yue , Yu Hai , Kang Hyeog , Gao Jin , Daniels Robert , Chen Xi 
Published: May 2024

AbstractSialosides containing C8‐modified sialic acids are challenging synthetic targets but potentially useful probes for diagnostic substrate profiling of sialidases and elucidating the binding specificity of sialic acid‐interacting proteins. Here, we demonstrate efficient chemoenzymatic methods for synthesizing para‐nitrophenol‐tagged α2–3‐ and α2–6‐linked sialyl galactosides containing C8‐acetamido, C8‐azido, or C8‐amino derivatized N‐acetylneuraminic acid (Neu5Ac). High‐throughput substrate specificity studies showed that the C8‐modification of sialic acid significantly changes its recognition by sialidases from humans, various bacteria, and different influenza A and B viruses. Sialosides carrying Neu5Ac with a C8‐azido modification were generally well tolerated by all the sialidases we tested, whereas sialosides containing C8‐acetamido‐modified Neu5Ac were only cleaved by selective bacterial sialidases. In contrast, sialosides with C8‐amino‐modified Neu5Ac were cleaved by a combination of selective bacterial and influenza A virus sialidases. These results indicate that sialosides terminated with a C8‐amino or C8‐acetamido‐modified sialic acid can be used with other sialosides for diagnostic profiling of disease‐causing sialidase‐producing pathogens.
ON–OFF Control of Marangoni Self‐propulsion via A Supra‐amphiphile Fuel and Switch
Authors: Zhu Guiqiang , Zhang Shu , Lu Guoxin , Peng Benwei , Lin Cuiling , Zhang Liqun , Shi Feng , Zhang Qian , Cheng Mengjiao 
Published: May 2024

AbstractMarangoni self‐propulsion refers to motion of liquid or solid driven by a surface tension gradient, and has applications in soft robots/devices, cargo delivery, self‐assembly etc. However, two problems remain to be addressed for motion control (e.g., ON–OFF) with conventional surfactants as Marangoni fuel: (1) limited motion lifetime due to saturated interfacial adsorption of surfactants; (2) in‐ situ motion stop is difficult once Marangoni flows are triggered. Instead of covalent surfactants, supra‐amphiphiles with hydrophilic and hydrophobic parts linked noncovalently, hold promise to solve these problems owing to its dynamic and reversible surface activity responsively. Here, we propose a new concept of ‘supra‐amphiphile fuel and switch’ based on the facile synthesis of disodium‐4‐azobenzene‐amino‐1,3‐benzenedisulfonate (DABS) linked by a Schiff base, which has amphiphilicity for self‐propulsion, hydrolyzes timely to avoid saturated adsorption, and provides pH‐responsive control over ON‐OFF motion. The self‐propulsion lifetime is extended by 50‐fold with DABS and motion control is achieved. The mechanism is revealed with coupled interface chemistry involving two competitive processes of interfacial adsorption and hydrolysis of DABS based on both experiments and simulation. The concept of ‘supra‐amphiphile fuel and switch’ provides an active solution to prolong and control Marangoni self‐propulsive devices for the advance of intelligent material systems.
A Cytochrome P450 Enzyme Catalyses Oxetane Ring Formation in Paclitaxel Biosynthesis
Authors: Li Changkang , Yin Xinxin , Wang Shuai , Sui Songyang , Liu Jimei , Sun Xincheng , Di Jinming , Chen Ridao , Chen Dawei , Han Yaotian , Xie Kebo , Dai Jungui 
Published: May 2024

AbstractOxetane synthase (TmCYP1), a novel cytochrome P450 enzyme from Taxus×media cell cultures, has been functionally characterized to efficiently catalyse the formation of the oxetane ring in tetracyclic taxoids. Transient expression of TmCYP1 in Nicotiana benthamiana using 2α,5α,7β,9α,10β,13α‐hexaacetoxytaxa‐4(20),11(12)‐diene (1) as a substrate led to the production of a major oxetane derivative, 1β‐dehydroxybaccatin IV (1 a), and a minor 4β,20‐epoxide derivative, baccatin I (1 b). However, feeding the substrate decinnamoyltaxinine J (2), a 5‐deacetylated derivative of 1, yielded only 5α‐deacetylbaccatin I (2 b), a 4β,20‐epoxide. A possible reaction mechanism was proposed on the basis of substrate‐feeding, 2H and 18O isotope labelling experiments, and density functional theory calculations. This reaction could be an intramolecular oxidation‐acetoxyl rearrangement and the construction of the oxetane ring may occur through a concerted process; however, the 4β,20‐epoxide might be a shunt product. In this process, the C5‐O‐acetyl group in substrate is crucial for the oxetane ring formation but not for the 4(20)‐epoxy ring formation by TmCYP1. These findings provide a better understanding of the enzymatic formation of the oxetane ring in paclitaxel biosynthesis.
Isothiourea‐Catalysed Acylative Dynamic Kinetic Resolution of Tetra‐substituted Morpholinone and Benzoxazinone Lactols
Authors: Zhu Haoxiang , Manchado Alejandro , Omar Farah Abdikani , McKay Aidan P. , Cordes David B. , Cheong Paul Ha‐Yeon , Kasten Kevin , Smith Andrew D. 
Published: May 2024

AbstractThe development of methods to allow the selective acylative dynamic kinetic resolution (DKR) of tetra‐substituted lactols is a recognised synthetic challenge. In this manuscript, a highly enantioselective isothiourea‐catalysed acylative DKR of tetra‐substituted morpholinone and benzoxazinone‐derived lactols is reported. The scope and limitations of this methodology have been developed, with high enantioselectivity and good to excellent yields (up to 89 %, 99 : 1 er) observed across a broad range of substrate derivatives incorporating substitution at N(4) and C(2), di‐ and spirocyclic substitution at C(5) and C(6), as well as benzannulation (>35 examples in total). The DKR process is amenable to scale‐up on a 1 g laboratory scale. The factors leading to high selectivity in this DKR process have been probed through computation, with an N−C=O⋅⋅⋅isothiouronium interaction identified as key to producing ester products in highly enantioenriched form.
Recent Progress in Using Covalent Organic Frameworks to Stabilize Metal Anodes for Highly‐Efficient Rechargeable Batteries
Authors: Sun Jianlu , Kang Fangyuan , Yan Dongbo , Ding Tangjing , Wang Yulong , Zhou Xiaosi , Zhang Qichun 
Published: May 2024

AbstractAlkali metals (e.g. Li, Na, and K) and multivalent metals (e.g. Zn, Mg, Ca, and Al) have become star anodes for developing high‐energy‐density rechargeable batteries due to their high theoretical capacity and excellent conductivity. However, the inevitable dendrites and unstable interfaces of metal anodes pose challenges to the safety and stability of batteries. To address these issues, covalent organic frameworks (COFs), as emerging materials, have been widely investigated due to their regular porous structure, flexible molecular design, and high specific surface area. In this minireview, we summarize the research progress of COFs in stabilizing metal anodes. First, we present the research origins of metal anodes and delve into their advantages and challenges as anodes based on the physical/chemical properties of alkali and multivalent metals. Then, special attention has been paid to the application of COFs in the host design of metal anodes, artificial solid electrolyte interfaces, electrolyte additives, solid‐state electrolytes, and separator modifications. Finally, a new perspective is provided for the research of metal anodes from the molecular design, pore modulation, and synthesis of COFs.
Properties of polylactic acid/gelatin/acetyl tributyl citrate blend materials
Authors: He Ruhui , Tao Yao , Luo Zhu , Yang Le , Liao Jingshun , Xu Mengxia , Yang Shenglong , Lin Yechun 
Published: May 2024

AbstractThe inherent brittleness and high cost of polylactic acid (PLA) hinder its further application. Developing low‐cost, flexible, and biodegradable gelatin (GEL)‐modified PLA is a way to broaden the application prospects of PLA applications. Acetyl tributyl citrate (ATBC) was added to overcome the process difficulty of PLA/GEL melt blending and toughening the blends. Maleic anhydride (MAH) grafted PLA (PLA‐g‐MAH) was prepared to improve the compatibility of the PLA/GEL/ATBC. Because of the interface, physical and chemical interaction induced by PLA‐g‐MAH, the compatibility among PLA, GEL, and ATBC was enhanced, which significantly improved the plasticizing efficiency of ATBC. Results showed that the elongation at break of the blends can be improved by 491%, 68 times higher than that of pristine PLA. Moreover, the modified blends did not break under the conditions of notch impact, which exhibited excellent toughness. The blends possessed a high degradation rate owing to the hydrophilic gelatin and PLA‐g‐MAH, significantly accelerated the degradation process of PLA. The prepared PLA/GEL/ATBC/PLA‐g‐MAH biomass blended plastics exhibited good comprehensive performance, with true sustainability and environmental friendliness.
Combination of NIR and UV‐LEDs enables physical and chemical drying of aqueous coating dispersions as new green technology
Authors: Appelhoff Lukas , Hornemann Nicolas , Schmidt Jochen , Krautz Anita , Strehmel Bernd 
Published: May 2024

AbstractHeptamethine based cyanines, namely 1,3,‐trimethyl‐2‐(2‐2[2‐phenylsulfanyl‐3‐[2‐(1,3,3‐trimethyl‐1,3,3‐trithyl‐1,3‐dihydro‐indol‐2‐ylidene)‐ethylidene]cyclohex‐1‐enyl]vinyl)‐3H‐indolium chloride (S1) and 2‐[2‐(2‐chloro‐[2‐[1,1‐dimethyl‐7‐sulfo‐3‐(4‐sulfobutyl)‐1,3‐dihydro‐benzo[e]indol‐2‐ylidene]‐ethylidene]cyclopent‐1‐enyl]vinyl]‐1,1‐dimethyl‐7‐sulfo‐3‐(4‐sulfobutyl)‐1Hbenzo[e]indolium hydroxide, inner salt, triethylammonium salt (S2), efficiently result in physical drying of an aqueous dispersion comprising a polyurethane binder. S2 possesses a water solubility of 40 g/L. A high‐intensity near‐infrared‐LED emitting at 820 nm with an intensity of 1 W/cm2 served as light source. The cyanine converted the light absorbed into heat by internal conversion needing less drying time compared to conventional drying. Water content after film formation showed less then 1%. In the second step, ultraviolet (UV) exposure with a LED emitting at 395 nm resulted in formation of semi‐interpenetrating polymer networks by crosslinking of the multifunctional (meth)acrylate operating as reactive diluent. Ethyl phenyl(2,4,6‐trimethylbenzoyl)phosphinate‐L served as effective UV‐photoinitiator. Furthermore, the UV‐exposure together with Norrish Type I and Type II photoinitator systems results in a very efficient bleaching of the green physical dried film. This contribution shows for the first time a new photonic hybrid technique describing successful replacement of an oven‐based process by a photonic based step that generates heat needed for drying.