bluuebunny/crossref_metadata_2025_split huggingface dataset:
Supramolecular Assemblies of Glycopeptides Enhance Gap Junction Maturation of Human Induced Pluripotent Stem Cell‐Derived Cardiomyocytes via Inducing Spheroids Formation to Optimize Cardiac Repair
Authors: Li Hekai , Ye Wenyu , Yu Bin , Yan Xin , Lin Yuhui , Zhan Jie , Chen Peier , Song Xudong , Yang Pingzhen , Cai Yanbin 
Published: June 2023

AbstractStem cell‐based therapies have demonstrated significant potential for use in heart regeneration. An effective paradigm for heart repair in rodent and large animal models is the transplantation of human induced pluripotent stem cell‐derived cardiomyocytes (hiPSC‐CMs). Despite this, the functional and phenotypical immaturity of 2D‐cultured hiPSC‐CMs, particularly their low electrical integration, poses a caveat for clinical translation. In this study, a supramolecular assembly of a glycopeptide containing a cell adhesion motif‐RGD, and saccharide‐glucose (Bio‐Gluc‐RGD) is designed to enable the 3D spheroid formation of hiPSC‐CMs, promoting cell‐cell and cell‐matrix interactions that occur during spontaneous morphogenesis. HiPSC‐CMs in spheroids are prone to be phenotypically mature and developed robust gap junctions via activation of the integrin/ILK/p‐AKT/Gata4 pathway. Monodispersed hiPSC‐CMs encapsulated in the Bio‐Gluc‐RGD hydrogel are more likely to form aggregates and, therefore, survive in the infarcted myocardium of mice, accompanied by more robust gap junction formation in the transplanted cells, and hiPSC‐CMs delivered with the hydrogels also displayed angiogenic effect and anti‐apoptosis capacity in the peri‐infarct area, enhancing their overall therapeutic efficacy in myocardial infarction. Collectively, the findings illustrate a novel concept for modulating hiPSC‐CM maturation by spheroid induction, which has the potential for post‐MI heart regeneration.
Acid and Hypoxia Tandem‐Activatable Deep Near‐Infrared Nanoprobe for Two‐Step Signal Amplification and Early Detection of Cancer
Authors: Zhou Sensen , Jiang Lei , Li Cheng , Mao Hui , Jiang Chunping , Wang Zhongxia , Zheng Xianchuang , Jiang Xiqun 
Published: June 2023

AbstractThe early detection of cancers can significantly change outcomes even with existing treatments. However, ~50% of cancers still cannot be detected until they reach an advanced stage, highlighting the great challenges in the early detection. Here, an ultrasensitive deep near‐infrared (dNIR) nanoprobe that is successively responsive to tumor acidity and hypoxia is reported. It is demonstrated that the new nanoprobe specifically detects tumor hypoxia microenvironment based on deep NIR imaging in ten different types of tumor models using cancer cell lines and patient‐tissue derived xenograft tumors. By combining the acidity and hypoxia specific two‐step signal amplification with a deep NIR detection, the reported nanoprobe enables the ultrasensitive visualization of hundreds of tumor cells or small tumors with a size of 260 µm in whole‐body imaging or 115 µm metastatic lesions in lung imaging. As a result, it reveals that tumor hypoxia can occur as early as the lesions contain only several hundred cancer cells.
Trap‐Assisted Charge Generation and Recombination in State‐of‐the‐Art Organic Photodetectors
Authors: Ma Xiao , Janssen René A. J. , Gelinck Gerwin H. 
Published: June 2023

AbstractThe performance of organic photodetectors is steadily improving, and the specific detectivity, as a key figure of merit, has reached values of 1012–1013 Jones, i.e., comparable to that of silicon diodes but still considerably lower than the intrinsic limit. As with other semiconductor devices, the electrical performance of state‐of‐the art organic photodiodes (OPDs) is presently determined to a high degree by the presence of chemical impurities or structural defects which create carrier trapping states within the bandgap of organic active layer. This review aims to provide a comprehensive and timely account of trap‐assisted charge generation and recombination in OPDs, with emphasis on the impact of these phenomena on photodetector performance parameters such as, noise and dark current density, responsivity, response speed, and ultimately, specific detectivity.
3D Printed Liquid Crystal Polymer Thermosiphon for Heat Transfer under Vacuum
Authors: Seshadri Bharath , Hischier Illias , Masania Kunal , Schlueter Arno 
Published: June 2023

AbstractA novel approach is presented to 3D print vacuum–tight polymer components using liquid crystal polymers (LCPs). Vacuum–tight components are essential for gas storage and passive heat transfer, but traditional polymer 3D printing methods often suffer from poor interfaces between layers and high free volume, compromising vacuum integrity. By harnessing the unique properties of LCPs, including low free volume and low melt viscosity, highly ordered domains are achieved through nematic alignment of polymer chains. Critical gas–barrier properties are demonstrated, even in thin, single–print line–walled samples ranging from 0.8 to 1.6 mm. A 200 mm evacuated thermosiphon is successfully printed, which exhibits a thermal resistance of up to 2.18 K/W and an effective thermal conductivity of up to 28 W/mK at 60 °C. These values represent a significant increase compared to the base LCP material. Furthermore, the geometric freedom, enabled by 3D printing through the fabrication of complex–shaped thermosiphons, is showcased. The authors study highlights the potential of LCPs as high–performance materials for 3D printing vacuum–tight components with intricate geometries, opening new avenues for functional design. An application of integrating 3D printed thermosiphons as selective heat transfer components in building envelopes is presented, contributing to greenhouse gas emissions mitigation in the construction sector.
Continuous Ultra‐Broadband Near‐Infrared Sc2O3‐Based Nanophosphor Realized by Spectral Bridge of Cr3+‐Yb3+‐Cr4+ for Multiple Optical Applications
Authors: Wang Yining , Shang Mengmeng , Huang Shuai , Sun Yixin , Zhu Yiying , Xing Xiaole , Dang Peipei , Lin Jun 
Published: June 2023

AbstractCr3+‐activated near‐infrared (NIR) phosphors are one of the most influential candidates for the new generation of intelligent NIR phosphor‐converted light‐emitting diode (pc‐LED) light sources. For spectral analysis, the broader the spectrum, the more useful information it contains. Herein, ultra‐broadband Cr‐activated Sc2O3 nanophosphors, which exhibit NIR ultra‐broadband from 650 to 1600 nm, are developed by the sol–gel method. This ultra‐broadband emission originates from the presence of Cr3+ and Cr4+, two luminescent centers confirmed by diffuse reflection spectra, electron paramagnetic resonance, time‐resolved photoluminescence spectra, and temperature‐dependent emission spectra. The nanophosphor exhibits excellent temperature‐sensing performance with SA = 4.102% K−1 and SR = 1.855% K−1. Co‐doping Yb3+ into Sc2O3 nanophosphors builds the Cr3+‐Yb3+‐Cr4+ model to bridge the spectral gap located at 1000 nm, forming a continuous NIR ultra‐broadband spectrum ranging from 650 to 1600 nm for the first time. Moreover, the introduction of Yb3+ improves the thermal stability of nanophosphors from 29.49% to 50.65% at 150 °C. The NIR transmission spectra of water, ethanol, and peanut oil demonstrate that Sc2O3:Cr3+‐Yb3+‐Cr4+ NIR nanophosphors favor potential applications in spectral analysis. The construction of a Cr3+‐Yb3+‐Cr4+ spectral bridge for realizing NIR ultra‐broadband phosphors based on cheap blue LEDs provides novel and effective insights.
Regioselective Synthesis of 1,4‐Dienes via Palladium‐Catalyzed Oxidative Allylation of N‐Tosylhydrazones
Authors: Jin Yangbin , Li Chunsheng , Wu Wanqing , Jiang Huanfeng 
Published: June 2023

AbstractA palladium‐catalyzed allylic C−H oxidative allylation of N‐tosylhydrazones to synthesize skipped 1,4‐dienes is demonstrated. This direct allylic alkylation reaction has excellent site selectivity, tolerates a wide range of functional groups, and affords 1,4‐dienes in moderate to good yield. Moreover, this olefination method allows the regio‐ and stereoselective synthesis of 1,4‐dienes containing a trisubstituted alkene. Preliminary mechanistic studies reveal that the reaction undergoes allylic C(sp3)−H activation and a subsequent carbene migratory insertion.
Confined Synthesis of Amorphous Al2O3 Framework Nanocomposites Based on the Oxygen‐Potential Diagram as Sulfur Hosts for Catalytic Conversion
Authors: Geng Pengbiao , Lin Yuxing , Du Meng , Wu Chunsheng , Luo Tianxing , Peng Yi , Wang Lei , Jiang Xinyuan , Wang Shuli , Zhang Xiuyun , Ni Lubin , Chen Shuangqiang , Shakouri Mohsen , Pang Huan 
Published: June 2023

AbstractSulfur cathodes in Li–S batteries suffer significant volumetric expansion and lack of catalytic activity for polysulfide conversion. In this study, a confined self‐reduction synthetic route is developed for preparing nanocomposites using diverse metal ions (Mn2+, Co2+, Ni2+, and Zn2+)‐introduced Al‐MIL‐96 as precursors. The Ni2+‐introduced Al‐MIL‐96‐derived nanocomposite contains a “hardness unit”, amorphous aluminum oxide framework, to restrain the volumetric expansion, and a “softness unit”, Ni nanocrystals, to improve the catalytic activity. The oxygen‐potential diagram theoretically explains why Ni2+ is preferentially reduced. Postmortem microstructure characterization confirms the suppressive volume expansion. The in situ ultraviolet–visible measurements are performed to probe the catalytic activity of polysulfide conversion. This study provides a new perspective for designing nanocomposites with “hardness units” and “softness units” as sulfur or other catalyst hosts.
Association between infectious exposures in infancy and epigenetic age acceleration in young adulthood in metropolitan Cebu, Philippines
Authors: McDade Thomas W. , Ryan Calen P. , Adair Linda S. , Lee Nanette R. , Carba Delia B. , MacIsaac Julia L. , Dever Kristy , Atashzay Parmida , Kobor Michael S. , Kuzawa Christopher W. 
Published: June 2023

AbstractObjectivesThe drivers of human life expectancy gains over the past 200 years are not well‐established, with a potential role for historical reductions in infectious disease. We investigate whether infectious exposures in infancy predict biological aging using DNA methylation‐based markers that forecast patterns of morbidity and mortality later in life.MethodsN = 1450 participants from the Cebu Longitudinal Health and Nutrition Survey—a prospective birth cohort initiated in 1983—provided complete data for the analyses. Mean chronological age was 20.9 years when venous whole blood samples were drawn for DNA extraction and methylation analysis, with subsequent calculation of three epigenetic age markers: Horvath, GrimAge, and DunedinPACE. Unadjusted and adjusted least squares regression models were evaluated to test the hypothesis that infectious exposures in infancy are associated with epigenetic age.ResultsBirth in the dry season, a proxy measure for increased infectious exposure in the first year of life, as well as the number of symptomatic infections in the first year of infancy, predicted lower epigenetic age. Infectious exposures were associated with the distribution of white blood cells in adulthood, which were also associated with measures of epigenetic age.ConclusionsWe document negative associations between measures of infectious exposure in infancy and DNA methylation‐based measures of aging. Additional research, across a wider range of epidemiological settings, is needed to clarify the role of infectious disease in shaping immunophenotypes and trajectories of biological aging and human life expectancy.
Cerebral edema associated with diabetic ketoacidosis: Two case reports
Authors: Namatame Kaoru , Igarashi Yutaka , Nakae Ryuta , Suzuki Go , Shiota Kohei , Miyake Nodoka , Ishii Hiromoto , Yokobori Shoji 
Published: June 2023

AbstractBackgroundDiabetic ketoacidosis (DKA) is associated with a high mortality rate, especially if cerebral edema develops during the disease course. It is rarer and more severe in adults than in children. We present cases of two patients with cerebral edema‐related DKA.Case presentationThe first patient was a 38‐year‐old man with diabetes mellitus who presented with DKA‐related disturbed consciousness. Although glycemic correction was performed slowly, he showed pupil dilation 11 h later. He underwent emergency ventricular drainage, but died of cerebral herniation. The second patient was a 25‐year‐old woman who presented with impaired consciousness secondary to DKA. Head computed tomography showed subarachnoid hemorrhage and cerebral edema. No related intraoperative findings were observed; it was concluded that the first computed tomography scan revealed pseudo‐subarachnoid hemorrhage.ConclusionDiabetic ketoacidosis‐related cerebral edema develops despite treatment according to guidelines and is difficult to predict. Therefore, adult patients should be treated cautiously during DKA management.
Gastric tube perforation penetrating the pericardium after esophagectomy that needed surgical repair
Authors: Akutsu Tomohiro , Endo Akira , Okuzawa Hiraaki , Suzuki Keisuke , Yonekawa Chisato , Hoshi Hiromasa , Otomo Yasuhiro 
Published: June 2023

AbstractBackgroundAs the prognosis of esophageal cancer surgery has improved, reports on postoperative complications of gastric tubes have increased. Among them, gastric tube ulcer perforation is infrequent but often severe and difficult to treat.Case PresentationA 73‐year‐old man had undergone thoracoscopic subtotal esophagectomy and laparoscopic‐assisted gastric tube reconstruction via the retrosternal route for thoracic esophageal cancer 8 years previously. He was transferred to our hospital with a diagnosis of gastric tube ulcer perforation, penetrating the pericardium. Emergency surgery was performed to remove the gastric tube, followed by immediate reconstruction by right colon interposition. The patient was discharged on postoperative day 142.ConclusionWe report a rare complication of gastric tube ulcer perforation, penetrating the pericardium, after esophagectomy for esophageal cancer. It was successfully treated with appropriate surgical management.
Integrated Cascade Nanozymes with Antisenescence Activities for Atherosclerosis Therapy
Authors: Liu Wanling , Zhang Yihong , Wei Gen , Zhang Minxuan , Li Tong , Liu Quanyi , Zhou Zijun , Du Yan , Wei Hui 
Published: June 2023

AbstractSenescent cells are the critical drivers of atherosclerosis formation and maturation. Mitigating senescent cells holds promise for the treatment of atherosclerosis. In an atherosclerotic plaque microenvironment, senescent cells interact with reactive oxygen species (ROS), promoting the disease development. Here, we hypothesize that a cascade nanozyme with antisenescence and antioxidant activities can serve as an effective therapeutic for atherosclerosis. An integrated cascade nanozyme with superoxide dismutase‐ and glutathione peroxidase‐like activities, named MSe1, is developed in this work. The obtained cascade nanozyme can attenuate human umbilical vein endothelial cell (HUVEC) senescence by protecting DNA from damage. It significantly weakens inflammation in macrophages and HUVECs by eliminating overproduced intracellular ROS. Additionally, the MSe1 nanozyme effectively inhibits foam cell formation in macrophages and HUVECs by decreasing the internalization of oxidized low‐density lipoprotein. After intravenous administration, the MSe1 nanozyme significantly inhibits the formation of atherosclerosis in apolipoprotein E‐deficient (ApoE−/−) mice by reducing oxidative stress and inflammation and then decreases the infiltration of inflammatory cells and senescent cells in atherosclerotic plaques. This study not only provides a cascade nanozyme but also suggests that the combination of antisenescence and antioxidative stress holds considerable promise for treating atherosclerosis.
Electrocatalytic Urea Synthesis with 63.5 % Faradaic Efficiency and 100 % N‐Selectivity via One‐step C−N coupling
Authors: Zhang Xiaoran , Zhu Xiaorong , Bo Shuowen , Chen Chen , Cheng Kai , Zheng Jianyun , Li Shuang , Tu Xiaojin , Chen Wei , Xie Chao , Wei Xiaoxiao , Wang Dongdong , Liu Yingying , Chen Pinsong , Jiang San Ping , Li Yafei , Liu Qinghua , Li Conggang , Wang Shuangyin 
Published: June 2023

AbstractElectrocatalytic urea synthesis via coupling N2 and CO2 provides an effective route to mitigate energy crisis and close carbon footprint. However, the difficulty on breaking N≡N is the main reason that caused low efficiencies for both electrocatalytic NH3 and urea synthesis, which is the bottleneck restricting their industrial applications. Herein, a new mechanism to overcome the inert of the nitrogen molecule was proposed by elongating N≡N instead of breaking N≡N to realize one‐step C−N coupling in the process for urea production. We constructed a Zn−Mn diatomic catalyst with axial chloride coordination, Zn−Mn sites display high tolerance to CO poisoning and the Faradaic efficiency can even be increased to 63.5 %, which is the highest value that has ever been reported. More importantly, negligible N≡N bond breakage effectively avoids the generation of ammonia as intermediates, therefore, the N‐selectivity in the co‐electrocatalytic system reaches100 % for urea synthesis. The previous cognition that electrocatalysts for urea synthesis must possess ammonia synthesis activity has been broken. Isotope‐labelled measurements and Operando synchrotron‐radiation Fourier transform infrared spectroscopy validate that activation of N−N triple bond and nitrogen fixation activity arise from the one‐step C−N coupling process of CO species with adsorbed N2 molecules.
A Click Chemistry‐Based Artificial Metallo‐Nuclease
Authors: Gibney Alex , de Paiva Raphael E. F. , Singh Vandana , Fox Robert , Thompson Damien , Hennessy Joseph , Slator Creina , McKenzie Christine J. , Johansson Pegah , McKee Vickie , Westerlund Fredrik , Kellett Andrew 
Published: June 2023

AbstractArtificial metallo‐nucleases (AMNs) are promising DNA damaging drug candidates. Here, we demonstrate how the 1,2,3‐triazole linker produced by the Cu‐catalysed azide‐alkyne cycloaddition (CuAAC) reaction can be directed to build Cu‐binding AMN scaffolds. We selected biologically inert reaction partners tris(azidomethyl)mesitylene and ethynyl‐thiophene to develop TC‐Thio, a bioactive C3‐symmetric ligand in which three thiophene‐triazole moieties are positioned around a central mesitylene core. The ligand was characterised by X‐ray crystallography and forms multinuclear CuII and CuI complexes identified by mass spectrometry and rationalised by density functional theory (DFT). Upon Cu coordination, CuII‐TC‐Thio becomes a potent DNA binding and cleaving agent. Mechanistic studies reveal DNA recognition occurs exclusively at the minor groove with subsequent oxidative damage promoted through a superoxide‐ and peroxide‐dependent pathway. Single molecule imaging of DNA isolated from peripheral blood mononuclear cells shows that the complex has comparable activity to the clinical drug temozolomide, causing DNA damage that is recognised by a combination of base excision repair (BER) enzymes.
Chiral Phosphoric Acid Catalyzed Asymmetric Hydrolysis of Biaryl Oxazepines for the Synthesis of Axially Chiral Biaryl Amino Phenol Derivatives
Authors: Wei Liwen , Li Jiaomeng , Zhao Yi , Zhou Qinglong , Wei Zhikang , Chen Yuhang , Zhang Xinglong , Yang Xing 
Published: June 2023

AbstractThe development of catalytic asymmetric reaction with water as the reactant is challenging due to the reactivity‐ and stereoselectivity‐control issues resulted from the low nucleophilicity and the small size of water. We disclose herein a chiral phosphoric acid (CPA) catalyzed atroposelective ring‐opening reaction of biaryl oxazepines with water. A series of biaryl oxazepines undergo the CPA catalyzed asymmetric hydrolysis in a highly enantioselective manner. The key for the success of this reaction is the use of a new SPINOL‐derived CPA catalyst and the high reactivity of biaryl oxazepine substrates towards water under acidic conditions. Density functional theory calculations suggest that the reaction proceeds via a dynamic kinetic resolution pathway and the CPA catalyzed addition of water to the imine group is both enantio‐ and rate‐determining.
Surface Adsorbed Hydroxyl: A Double‐Edged Sword in Electrochemical CO2 Reduction over Oxide‐Derived Copper
Authors: Wei Daixing , Wang Yiqing , Dong Chung‐Li , Thi Thuy Nga Ta , Shi Yuchuan , Wang Jialin , Zhao Xiaoli , Dong Fan , Shen Shaohua 
Published: June 2023

AbstractOxide‐derived Cu (OD−Cu) featured with surface located sub‐20 nm nanoparticles (NPs) created via surface structure reconstruction was developed for electrochemical CO2 reduction (ECO2RR). With surface adsorbed hydroxyls (OHad) identified during ECO2RR, it is realized that OHad, sterically confined and adsorbed at OD−Cu by surface located sub‐20 nm NPs, should be determinative to the multi‐carbon (C2) product selectivity. In situ spectral investigations and theoretical calculations reveal that OHad favors the adsorption of low‐frequency *CO with weak C≡O bonds and strengthens the *CO binding at OD−Cu surface, promoting *CO dimerization and then selective C2 production. However, excessive OHad would inhibit selective C2 production by occupying active sites and facilitating competitive H2 evolution. In a flow cell, stable C2 production with high selectivity of ∼60 % at −200 mA cm−2 could be achieved over OD−Cu, with adsorption of OHad well steered in the fast flowing electrolyte.
Rhodium‐Catalyzed Regio‐ and Diastereoselective [3+2] Cycloaddition of gem‐Difluorinated Cyclopropanes with Internal Olefins
Authors: Zeng Yaxin , Xia Ying 
Published: June 2023

AbstractDirect synthesis of gem‐difluorinated carbocyclic molecules represents a longstanding challenge in organic chemistry. Herein, a Rh‐catalyzed [3+2] cycloaddition reaction between readily available gem‐difluorinated cyclopropanes (gem‐DFCPs) and internal olefins has been developed, enabling the efficient synthesis of gem‐difluorinated cyclopentanes with good functional group compatibility, excellent regioselectivity and good diastereoselectivity. The resulting gem‐difluorinated products can undergo downstream transformations to access various mono‐fluorinated cyclopentenes and cyclopentanes. This reaction demonstrates the use of gem‐DFCPs as a type of “CF2” C3 synthon for cycloaddition under transition metal catalysis, which provides potential strategy for synthesizing other gem‐difluorinated carbocyclic molecules.
Oxa‐TriQuinoline: A New Entry to Aza‐Oxa‐Crown Architectures**
Authors: Kobayashi Toi , Kumagai Naoya 
Published: June 2023

AbstractA new 15‐membered‐macrocyclic molecular entity, oxa‐TriQuinoline (o‐TQ), was designed and synthesized. In o‐TQ, three oxygen atoms were joined onto three quinoline units at the 2‐ and 8‐positions in a head‐to‐tail fashion by three‐fold SNAr reactions, giving rise to the characteristic N3O3 aza‐oxa‐crown architecture. o‐TQ can serve as a new tridentate nitrogen ligand to capture a CuI cation and adopt a bowl shape, before supramolecular complexation with corannulene and [12]cycloparaphenylene (CPP) occurs through π–π and CH–π interactions. In the presence of the CuI cation, the non‐emissive o‐TQ becomes a highly emissive material in the solid state, whereby the emission wavelengths depend on the ancillary ligand on the CuI cation. The o‐TQ/CuI complex is able to promote carbene catalysis to provide a range of enamines with a gem‐difluorinated terminus.