bluuebunny/crossref_metadata_2025_split huggingface dataset:
Engineered Cell Membrane‐Coated Nanoparticles: New Strategies in Glioma Targeted Therapy and Immune Modulation
Authors: Ma Yilei , Yi Jia , Ruan Jing , Ma Jiahui , Yang Qinsi , Zhang Kun , Zhang Maolan , Zeng Guoming , Jin Libo , Huang Xiaobei , Li Jianshu , Yang Haifeng , Wu Wei , Sun Da 
Published: April 2024

AbstractGliomas, the most prevalent primary brain tumors, pose considerable challenges due to their heterogeneity, intricate tumor microenvironment (TME), and blood‐brain barrier (BBB), which restrict the effectiveness of traditional treatments like surgery and chemotherapy. This review provides an overview of engineered cell membrane technologies in glioma therapy, with a specific emphasis on targeted drug delivery and modulation of the immune microenvironment. This study investigates the progress in engineered cell membranes, encompassing physical, chemical, and genetic alterations, to improve drug delivery across the BBB and effectively target gliomas. The examination focuses on the interaction of engineered cell membrane‐coated nanoparticles (ECM‐NPs) with the TME in gliomas, emphasizing their potential to modulate glioma cell behavior and TME to enhance therapeutic efficacy. The review further explores the involvement of ECM‐NPs in immunomodulation techniques, highlighting their impact on immune reactions. While facing obstacles related to membrane stability and manufacturing scalability, the review outlines forthcoming research directions focused on enhancing membrane performance. This review underscores the promise of ECM‐NPs in surpassing conventional therapeutic constraints, proposing novel approaches for efficacious glioma treatment.
Hypoxia‐Responsive Hydrogen‐Bonded Organic Framework‐Mediated Protein Delivery for Cancer Therapy
Authors: He Xu , Wang Jian , Liu Xiao , Niu Qingyu , Li Zhiqiang , Chen Banglin , Xiong Qingqing 
Published: April 2024

AbstractThe efficient delivery of therapeutic proteins to tumor sites is a promising cancer treatment modality. Hydrogen‐bonded organic frameworks (HOFs) are successfully used for the protective encapsulation of proteins; however, easy precipitation and lack of controlled release of existing HOFs limit their further application for protein delivery in vivo. Here, a hypoxia‐responsive HOF, self‐assembled from azobenzenedicarboxylate/polyethylene glycol‐conjugated azobenzenedicarboxylate and tetrakis(4‐amidiniumphenyl)methane through charge‐assisted hydrogen‐bonding, is developed for systemic protein delivery to tumor cells. The newly generated HOF platform efficiently encapsulates representative cytochrome C, demonstrating good dispersibility under physiological conditions. Moreover, it can respond to overexpressed reductases in the cytoplasm under hypoxic conditions, inducing fast intracellular protein release to exert therapeutic effects. The strategy presented herein can be applied to other therapeutic proteins and can be expanded to encompass more intrinsic tumor microenvironment stimuli. This offers a novel avenue for utilizing HOFs in protein‐based cancer therapy.
Closed Twisted Hydrogel Ribbons with Self‐Sustained Motions under Static Light Irradiation
Authors: Zhu Qing Li , Liu Weixuan , Khoruzhenko Olena , Breu Josef , Bai Huiying , Hong Wei , Zheng Qiang , Wu Zi Liang 
Published: April 2024

AbstractSelf‐sustained motions are widespread in biological systems by harvesting energy from surrounding environments, which inspire scientists to develop autonomous soft robots. However, most‐existing soft robots require dynamic heterogeneous stimuli or complex fabrication with different components. Recently, control of topological geometry has been promising to afford soft robots with physical intelligence and thus life‐like motions. Reported here are a series of closed twisted ribbon robots, which exhibit self‐sustained flipping and rotation under constant light irradiation. Both Möbius strip and Seifert ribbon robots are devised for the first time by using an identical hydrogel, which responds to light irradiation on either side. Experiment and simulation results indicate that the self‐regulated motions of the hydrogel robots are related to fast and reversible response of muscle‐like gel, self‐shadowing effect, and topology‐facilitated refresh of light‐exposed regions. The motion speeds and directions of the hydrogel robots can be tuned over a wide range. These closed twisted ribbon hydrogels are further applied to execute specific tasks in aqueous environments, such as collecting plastic balls, climbing a vertical rod, and transporting objects. This work presents new design principle for autonomous hydrogel robots by benefiting from material response and topology geometry, which may be inspirative for the robotics community.
Manipulating Single‐Molecule Exciplex TADF and Deep‐Blue RTP Through Non‐Covalent π–π Interaction in a Molecular Foldamer
Authors: Huang Rongjuan , Yu Kaixin , Chen Shunwei , Chen Kuan , Luo Yanju , Lu Zhiyun , Dias Fernando B. , Zheng Xujun 
Published: April 2024

AbstractAlthough the π–π stacking has been widely applied for constructing aggregated emitters in optoelectronics fields, the role of intramolecular non‐covalent π–π interactions has not been well studied. Here, a supramolecular foldermer M‐σ‐C, with the electron donor (D) and acceptor (A) units spatially separated with a non‐covalent bond at a close distance by methylene linker is designed and synthesized. This gives a face‐to‐face D/A stacking configuration with supramolecular π–π interactions. Temperature‐dependent nuclear magnetic resonance measurements and single crystal analyses confirm its folding configuration. In solutions, M‐σ‐C exhibits a single‐molecule exciplex thermally activated delayed fluorescence (TADF) property ascribing to the efficient intramolecular through‐space charge transfer (CT) process. While single‐molecule deep‐blue room temperature phosphorescence (RTP) with a long afterglow lifetime of 236 ms is observed in a nonpolar matrix, which represents the record lifetime among current 3CT‐character featured RTP. This work indicates that intramolecular non‐covalent interactions play an important role in manipulating high‐performance single‐molecule exciplex TADF and RTP, and provide a feasible molecular design strategy for supramolecular chemistry involving the development of optoelectronic materials.
Access to γ‐Iodo‐gem‐Diborylated Cyclopentanes and to Bicyclic Cyclopropanes
Authors: Circule Dace , Dénès Fabrice , Renaud Philippe 
Published: April 2024

AbstractA formal atom transfer radical [3+2] annulation (ATRAn) reaction between different homoallyl radical precursors and 1,1‐diborylethene was developed. It provides a rapid access to polysubstituted cyclopentanes containing a gem‐diboronic ester moiety. The synthetic utility of theses uniquely functionalized 5‐membered rings is highlighted by their easy conversion to attractive borylated building blocks such as 1‐borylated bicyclo[3.1.0]hexanes. The ATRAn reaction was extended to homopropagylic radicals giving access to unique allylic gem‐diboronic esters that could be used in allylboration of aldehydes. Furthermore, this work highlights that 1,1‐diborylethene represents a synthetic equivalent to ketene, a so far elusive radical trap due to its daunting reactivity.
Engineering Photothermal Catalytic CO2 Nanoreactor for Osteomyelitis Treatment by In Situ CO Generation
Authors: Zhuang Fan , Jing Luxia , Xiang Huijing , Li Cuixian , Lu Beilei , Yan Lixia , Wang Jingjing , Chen Yu , Huang Beijian 
Published: April 2024

AbstractPhotocatalytic carbon dioxide (CO2) reduction is an effective method for in vivo carbon monoxide (CO) generation for antibacterial use. However, the available strategies mainly focus on utilizing visible‐light‐responsive photocatalysts to achieve CO generation. The limited penetration capability of visible light hinders CO generation in deep‐seated tissues. Herein, a photothermal CO2 catalyst (abbreviated as NNBCs) to achieve an efficient hyperthermic effect and in situ CO generation is rationally developed, to simultaneously suppress bacterial proliferation and relieve inflammatory responses. The NNBCs are modified with a special polyethylene glycol and further embellished by bicarbonate (BC) decoration via ferric ion‐mediated coordination. Upon exposure to 1064 nm laser irradiation, the NNBCs facilitated efficient photothermal conversion and in situ CO generation through photothermal CO2 catalysis. Specifically, the photothermal effect accelerated the decomposition of BC to produce CO2 for photothermal catalytic CO production. Benefiting from the hyperthermic effect and in situ CO production, in vivo assessments using an osteomyelitis model confirmed that NNBCs can simultaneously inhibit bacterial proliferation and attenuate the photothermal effect‐associated pro‐inflammatory response. This study represents the first attempt to develop high‐performance photothermal CO2 nanocatalysts to achieve in situ CO generation for the concurrent inhibition of bacterial growth and attenuation of inflammatory responses.
Bioinspired menstrual blood‐derived stem cells‐conditioned medium/polymersome nanoparticles for the treatment of carbon tetrachloride‐induced acute liver failure in mice
Authors: Li Zuhong , Li Qian , Ouyang Xiaoxi , Tang Shima , Liu Qiuhong , Zhang Yaqi , Zhang Yanhong , Yu Xiaopeng , Zhu Danhua , Mu Ying , Li Lanjuan 
Published: April 2024

AbstractAcute liver failure is a life‐threatening syndrome, for which liver transplantation is presently the most effective treatment. Unfortunately, such treatment is extremely limited by a shortage of donor organs. Stem cell therapy offers a promising treatment strategy for acute liver failure. Yet, therapeutic efficacy and potential are hampered by administration route and safety concerns. In this work, we fabricated menstrual blood‐derived stem cells‐conditioned medium/polymersome hybrid nanoparticles that were self‐assembled from amphiphilic block copolymers via the direct hydration method and encapsulated therapeutic bioactive factors within the aqueous core of vesicles. The merit of vesicular architecture enabled the loading capacity of distinct proteins and the maintenance of biological activity. These hybrid nanoparticles can be steadily taken up into cytoplasm and promote hepatocyte proliferation in vitro. Prolonged in vivo circulation time brought higher accumulation in livers. The therapeutic nanoparticles alleviated hepatic injury and promoted liver recovery in mice with carbon tetrachloride‐induced liver failure. Considering the feasibility and benefit of the hybrid nanoparticle therapy, it provided a potential strategy to treat acute liver failure.
Discovery of Alloy Catalysts Beyond Pd for Selective Hydrogenation of Reformate via First‐Principle Screening with Consideration of H‐Coverage
Authors: Wang Jiayi , Xu Haoxiang , Zhang Yihao , Wu Jianguo , Ma Haowen , Zhan Xuecheng , Zhu Jiqin , Cheng Daojian 
Published: April 2024

AbstractThe highly selective hydrogenation to remove olefins is a significant refining approach for the reformate. Herein, a library of transition metal for reformate hydrogenation is tested experimentally to validate the predictive level of catalytic activity from our theoretical framework, which combines ab initio calculations and microkinetic modeling, with consideration of surface H‐coverage effect on hydrogenation kinetics. The favorable H coverage of specific alloy surface under relevant hydrogenation condition, is found to be determined by its corresponding alloy composition. Besides, olefin hydrogenation rate is determined as a function of two descriptors, i.e. H coverage and binding energies of atomic hydrogen, paving the way to computationally screen on metal component in the periodic table. Evaluation of 172 bimetallic alloys based on the activity volcano map, as well as benzene hydrogenation rate, identifies prospective superior candidates and experimentally confirms that Zn3Ir1 outperforms pure Pd catalysts for the selective hydrogenation refining of reformate. The insights into H‐coverage‐related microkinetic modelling have enabled us to both theoretically understand experimental findings and identify novel catalysts, thus, bridging the gap between first‐principle simulations and industrial applications. This work provides useful guidance for experimental catalyst design, which can be easily extended to other hydrogenation reaction.
Nickel‐Catalyzed Chemoselective Carbomagnesiation for Atroposelective Ring‐Opening Difunctionalization
Authors: Sun Tingting , Guo Linchao , Li Qi , Cao Zhi‐Chao 
Published: April 2024

AbstractThere is a pressing need for methods that can connect enantioenriched organic compounds with readily accessible building blocks via asymmetric functionalization of unreactive chemical bonds in organic synthesis and medicinal chemistry. Herein, the asymmetric chemoselective cleavage of two unactivated C(Ar)−O bonds in the same molecule is disclosed for the first time through an unusual nickel‐catalyzed carbomagnesiation. This reaction facilitates the evolution of a novel atroposelective ring‐opening difunctionalization. Utilizing readily available dibenzo bicyclic substrates, diverse valuable axially chiral biaryls are furnished with high efficiencies. Synthetic elaborations showcase the application potential of this method. The features of this method include good atom‐economy, multiple roles of the nucleophile, and a simple catalytic system that enables the precise magnesiation of an α‐C(Ar)−O bond and arylation of a β‐C(Ar)−O bond.
Noncovalent Interaction Guided Precise Photoluminescence Regulation of Gold Nanoclusters in Both Isolate Species and Aggregate States
Authors: Luo Xiaoxi , Kong Jie , Xiao Hang , Sang Dongmiao , He Kui , Zhou Meng , Liu Jinbin 
Published: April 2024

AbstractDesigning luminophores bright in both isolate species and aggregate states is of great importance in many emerging cutting‐edge applications. However, the conventional luminophores either emit in isolate species but quench in aggregate state or emit in aggregate state but darken in isolate species. Here we demonstrate that the precise regulation of noncovalent interactions can realize luminophores bright in both isolate species and aggregate states. It is firstly discovered that the intra‐cluster interaction enhances the emission of atomically precise Au25(pMBA)18 (pMBA=4‐mercaptobenzoic acid), a nanoscale luminophore, while the inter‐cluster interaction quenches the emission. The emission enhancing strategies are then well‐designed by both introducing exogenous substances to block inter‐cluster interaction and surface manipulation of Au25(pMBA)18 at the molecular level to enhance intra‐cluster interaction, opening new possibilities to controllably enhance the luminophore's photoluminescence in both isolate species and aggregate states in different phases including aqueous solution, solid state and organic solvents.
Acceptor‐Reactivity‐Controlled Stereoconvergent Synthesis and Immunological Activity of a Unique Pentasaccharide from the Cell Wall Polysaccharide of Cutibacterium acnes C7
Authors: Hao Tianhui , Feng Ke , Jin Hongzhen , Li Jiawei , Zhou Chenkai , Liu Xingbang , Zhao Wei , Yu Fan , Li Tiehai 
Published: April 2024

AbstractBacterial cell‐surface polysaccharides are involved in various biological processes and have attracted widespread attention as potential targets for developing carbohydrate‐based drugs. However, the accessibility to structurally well‐defined polysaccharide or related active oligosaccharide domains remains challenging. Herein, we describe an efficiently stereocontrolled approach for the first total synthesis of a unique pentasaccharide repeating unit containing four difficult‐to‐construct 1,2‐cis‐glycosidic linkages from the cell wall polysaccharide of Cutibacterium acnes C7. The features of our approach include: 1) acceptor‐reactivity‐controlled glycosylation to stereoselectively construct two challenging rare 1,2‐cis‐ManA2,3(NAc)2 (β‐2,3‐diacetamido‐2,3‐dideoxymannuronic acid) linkages, 2) combination use of 6‐O‐tert‐butyldiphenylsilyl (6‐O‐TBDPS)‐mediated steric shielding effect and ether solvent effect to stereoselectively install a 1,2‐cis‐glucosidic linkage, 3) bulky 4,6‐di‐O‐tert‐butylsilylene (DTBS)‐directed glycosylation to stereospecifically construct a 1,2‐cis‐galactosidic linkage, 4) stereoconvergent [2+2+1] and one‐pot chemoselective glycosylation to rapidly assemble the target pentasaccharide. Immunological activity tests suggest that the pentasaccharide can induce the production of proinflammatory cytokine TNF‐α in a dose‐dependent manner.
Coral‐Inspired Terahertz‐Infrared Bi‐Stealth Electronic Skin
Authors: Li Shangjing , Pan Kaichao , Du Jiang , Liu Zunfeng , Qiu Jun 
Published: April 2024

AbstractThe development of electronic skin with dual stealth functionality is crucial for enabling devices to operate effectively in dynamic electromagnetic environments, thereby facilitating intelligent electromagnetic protection for autonomous perception. However, achieving compatibility between terahertz (THz) and infrared (IR) stealth technologies remains largely unexplored due to their inherent contradictions. Herein, inspired by natural corals, a novel coral‐like multi‐scale composite foam (CMSF) was proposed that ingeniously reconciles these contradictions. The design capitalizes on the conductive network and heat insulation properties of the foam skeleton, the loss effects and low infrared emission of metal particles, and the infrared transparency of magneto‐optical materials. This approach leads to the realization of a THz‐IR bi‐stealth electronic skin concept. The CMSF exhibits a maximum reflection loss of 84.8 dB in the terahertz band, while its infrared stealth capability ensures environmental adaptability under varying temperatures. Furthermore, the electronic skin exhibits exceptional sensitivity and reliability as a wearable device for perceiving environmental changes. This advanced material, combining multispectral stealth with sensing capabilities, holds immense potential for applications ranging from camouflage technology to smart wearables.
Evaluating long‐term trends in annual precipitation: A temporal consistency analysis of ERA5 data in the Alps and Italy
Authors: Lussana Cristian , Cavalleri Francesco , Brunetti Michele , Manara Veronica , Maugeri Maurizio 
Published: April 2024

AbstractReanalyses are utilized for calculating climatological trends due to their focus on temporal consistency. ERA5 reanalysis family has proven to be a valuable and widely used product for trend extraction. This study specifically examines long‐term trends in total annual precipitation across two climatic hotspots: the Alps and Italy. It is acknowledged by reanalysis producers that variations in the observational systems used for data assimilation impact water cycle components like precipitation. This understanding highlights the need of assessing to what extent temporal variations in ERA5 precipitation amounts are solely a result of climate variations and the influence of changes in the observational system impacting simulation accuracy. Our research examines the differences between ERA5 and similar reanalyses against homogenized, trend‐focused observational datasets. We find that discerning the climatological signal within ERA5 adjustments for observational system variations is challenging. The trend in ERA5 from 1940 to 1970 shows distinct patterns over the Alps and, to a lesser extent, Italy, diverging from later ERA5 trends and those in other reanalyses. Notably, ERA5 shows an increasing, although nonlinear, trend in the deviation between ERA5 and the observational datasets. Improving future reanalysis interpretability could involve adopting a model‐only integration for the same period, akin to the ERA‐20C and ERA‐20CM approach.
Stabilization of galactose oxidase by high hydrostatic pressure: Insights on the role of cavities size
Authors: Kang Min J. , Reyes‐De‐Corcuera José I. 
Published: April 2024

AbstractHigh hydrostatic pressure stabilized galactose oxidase (GaOx) at 70.0–80.0°C against thermal inactivation. The pseudo‐first‐order rate constant of inactivation kinact decreased by a factor of 8 at 80°C and by a factor of 44 at 72.5°C. The most pronounced effect of pressure was at the lowest studied temperature of 70.0°C with an activation volume of inactivation ΔV‡ of 78.8 cm3 mol−1. The optimal pressure against thermal inactivation was between 200 and 300 MPa. Unlike other enzymes, as temperature increased the ΔV‡ of inactivation decreased, and as pressure increased the activation energy of inactivation Eai increased. Combining the results for GaOx with earlier research on the pressure‐induced stabilization of other enzymes suggests that ΔV‡ of inactivation correlates with the total molar volume of cavities larger than ~100 Å3 in enzyme monomers for enzymes near the optimal pH and whose thermal unfolding is not accompanied by oligomer dissociation.
Exploring young people with eating difficulties and their caregivers' experiences of person‐centred counselling
Authors: Ward Samantha , Daughtrey Nicola , Constable Chloe , Bell Judith 
Published: April 2024

AbstractBackgroundThere has been a significant increase in the number of young people with eating difficulties (EDs), and current waiting times are not meeting the standard recommended by the National Health Service. Therefore, TIC+, a mental health charity in Gloucestershire, launched an ED counselling service, TEDS. The service aimed to promptly provide young people with person‐centred counselling as an alternative option for support.AimsVery few studies have investigated the experience of individuals with EDs who are engaging with person‐centred counselling, and exploration of this can help us to ascertain whether the approach should be more widely deployed while also informing service development for TEDS.Materials and MethodsThis study qualitatively explored young people and their caregivers' experiences of the service using semi‐structured interviews; four young people and four caregivers took part. Data were analysed using thematic analysis.ResultsThe findings revealed that the person‐centred counselling provided was valuable for young people, with improvements to their EDs evident.DiscussionHowever, there were several barriers to counselling that must be addressed. Furthermore, caregivers experienced a sense of loss of control and helplessness, which may have ramifications for young people too, demonstrating a need to consider how best to support caregivers.ConclusionThere is preliminary support for the use of person‐centred counselling for young people with eating difficulites.
Effect of Alkali Metal Cations and Trace Metal Impurities on Cathodic Corrosion of Gold Electrode Surfaces
Authors: Elnagar Mohamed M. , Kibler Ludwig A. , Jacob Timo 
Published: April 2024

AbstractIn this work, we comprehensively studied the cathodic corrosion of Au electrodes as a function of the identity of alkali metal hydroxides at different concentrations and various negative potentials. We reveal that the ratio of free water and water bound in hydration shells controls the overall cathodic corrosion behavior, alongside the specific adsorption of alkali metal cations. Moreover, we highlight the crucial role of electrolyte cleanliness, particularly regarding the presence of trace metal impurities. Interestingly, the presence of trace amounts of nickel and iron in as‐received CsOH suppresses cathodic corrosion by their deposition onto Au surfaces. In contrast, after purification the polarization of Au surfaces in 10 M CsOH leads to the formation of nanoporous surfaces with high electrochemically active surface area, in which the degree of porosity can be tuned by varying the polarization time at −1.6 V vs. RHE.