bluuebunny/crossref_metadata_2025_split huggingface dataset:
Reductive Photocatalytic Proton‐Coupled Electron Transfer by a Zirconium‐Based Molecular Platform
Authors: Jabalera‐Ortiz Pedro J. , Perona Cristina , Moreno‐Albarracín Mercedes , Carmona Francisco J. , Jiménez Juan‐Ramón , Navarro Jorge A. R. , Garrido‐Barros Pablo 
Published: October 2024

AbstractReductive proton‐coupled electron transfer (PCET) has important energetic implications in numerous synthetic and natural redox processes. The development of catalytic systems that can mediate such transformations has become an attractive target, especially when light is used to generate the reactive species towards solar‐to‐chemicals conversion. However, such approach becomes challenged by kinetic competition with H2 evolution. Here we describe the excited state reactivity of a molecular Zr‐based platform under visible light irradiation for the efficient reduction of multiple bonds. Mechanistic investigations shine light on a charge separation process that colocalizes an excited electron and an acidic proton to promote selective PCET. We further leveraged this reactivity for the photocatalytic reduction of a variety of organic substrates. Our results demonstrate the promise of this molecular platform to design strong photocatalytic PCET mediators for reductive transformations. More broadly, we also show the potential relevance of PCET mechanisms in the (photo)redox chemistry of Zr‐based molecular materials.
Arenicolide Family Macrolides Provide a New Therapeutic Lead Combating Multidrug‐Resistant Tuberculosis
Authors: Hwang Sunghoon , Heo Bo Eun , Nguyen Thanh Quang , Kim Young Jae , Lee Sung‐Gwon , Huynh Thanh‐Hau , Kim Eunji , Jo Shin‐Il , Baek Min‐Jun , Shin Eun‐Kyung , Oh Joonseok , Park Chungoo , Yoon Yeo Joon , Park Eun‐Jin , Kim Kyung Tae , Ryoo Sungweon , Lee Da‐Gyum , Wood Connor , Woo Minjeong , Kim Dae‐Duk , Paik Seungwha , Jo Eun‐Kyeong , Jang Jichan , Oh Dong‐Chan 
Published: October 2024

AbstractThe emergence of multidrug‐resistant (MDR) and extensively drug‐resistant (XDR) strains of Mycobacterium tuberculosis (Mtb) poses a significant threat to health globally. During searching for new chemical entities regulating MDR‐ and XDR‐Mtb, chemical investigation of the black oil beetle gut bacterium Micromonospora sp. GR10 led to the discovery of eight new members of arenicolides along with the identification of arenicolide A (Ar−A, 1), which was a previously reported macrolide with incomplete configuration. Genomic analysis of the bacterial strain GR10 revealed their putative biosynthetic pathway. Quantum mechanics‐based computation, chemical derivatizations, and bioinformatic analysis established the absolute stereochemistry of Ar−A and arenicolides D−K (Ar−D−K, 2–9) completely for the first time. Biological studies of 1–9 revealed their antimicrobial activity against MDR and XDR strains of Mtb. Ar−A had the most potent in vitro antimicrobial efficacy against MDR‐ and XDR‐Mtb. Mechanistically, Ar−A induced ATP depletion and destabilized Mtb cell wall, thereby inhibiting growth. Notably, Ar−A exerted a significant antimicrobial effect against Mtb in macrophages, was effective in the treatment of Mtb infections, and showed a synergistic effect with amikacin (AMK) in a mouse model of MDR‐Mtb lung infection. Collectively, our findings indicate Ar−A to be a promising drug lead for drug‐resistant tuberculosis.
Catalyst‐Free Diborylation and Silaboration of Azoarenes: A Simple Photoinduced Approach
Authors: Mondal Reetu Rani , Pal Apurba Kumar , Geetharani K. 
Published: October 2024

AbstractThe diborylation of the N=N double bond of azoarenes has been achieved using a commercially available diboron reagent, B2cat2 [bis(catecholato)diboron]. By utilizing the photo‐switchable nature of azoarenes under blue‐LED light irradiation, an uncatalyzed diborylation and silaboration yielded a broad range of functionalized hydrazine derivatives. The mechanistic origin validates the importance of cis configuration, which is corroborated by theoretical calculations.
Intracellular Redox Environment Determines Cancer‐normal Cell Selectivity of Selenium Nanoclusters
Authors: Xiong Zushuang , He Lizhen , Pi Fen , Yu Yanzi , Xiao Zhirong , Chen Tianfeng 
Published: October 2024

AbstractElucidating the chemical structure and intracellular action mechanisms is still the critical limit for the clinical translation of nanomedicines. Intracellular redox environments originating from cell metabolism are key factors affecting internalized drug efficacy. Herein, we engineer Se−Se/Se−S bond to assemble selenium (Se) nanoclusters (SeClus) with intracellular redox environment‐driven selective structure. Chemical structure analysis reveals that, the bonding of sulfur atom in intermediates to the two neighboring or interposition Se atoms in Se rings is the key internal driving force for SeClus formation. This nanocluster can be predominantly transformed to selenocysteine to facilitate selenoproteins synthesis in normal cells, while metabolize to cytotoxic SeO32− based on the oxidative intracellular redox environment of cancer cells. Resultantly, SeClus exhibit significant cell proliferation inhibition ability to cancer cells and impressive safety to normal cells. Taken together, this study not only clarifies the chemical nature of the atom engineering of SeClus, but also elucidates its intracellular redox environment‐oriented anticancer mechanism.
Precise Regulation of the Reverse Intersystem Crossing Pathway by Hybridized Long‐Short Axis Strategy for High‐Performance Multi‐Resonance TADF Emitters
Authors: Liu Futong , Cheng Zhuang , Dong Wei , Yan Yan , Xu Yangze , Su Zihan , Hu Yin , Wan Liang , Lu Ping 
Published: October 2024

AbstractMulti‐resonance thermally activated delayed fluorescence (MR‐TADF) molecules have experienced great success in organic light‐emitting diodes (OLEDs) owing to their outstanding quantum efficiencies and narrow full width at half‐maximums (FWHMs). However, the reverse intersystem crossing (RISC) rates of MR‐TADF emitters are usually small, which will lead to relatively long triplet exciton lifetime and severe efficiency roll‐off. Here, we report an effective molecular design strategy to introduce multichannel RISC pathways and thus increase RISC rates without compromising the color fidelity and emission efficiency by the “hybridized long‐short axis (HLSA)” strategy. The TPA‐CN‐BN shows a near‐unity photoluminescence quantum yield, rapid RISC rate of 1.4×105 s−1, narrow FWHM of 23 nm, and small singlet‐triplet energy gap (ΔEST) of 0.06 eV in solution. The non‐sensitized OLED based on TPA‐CN‐BN exhibits a narrowband emission with the FWHM of 31 nm, in company with external quantum efficiency (EQE) of 37.9 %. Notably, the device exhibits the low efficiency roll‐off as the EQEs maintain 34.8 % and 21.8 % at 100 and 1000 cd m−2, respectively, representing the best performance for single‐host OLEDs based on the BCzBN skeleton. This study provides a fresh and promising approach to realize high‐performance OLEDs with high color purity and remarkable device efficiency.
A Mechanical Immune Checkpoint Inhibitor Stiffens Tumor Cells to Potentiate Antitumor Immunity
Authors: Zhao Yu , Hou Xiaoxue , Wang Zeyu , Peng Shiyu , Zheng Chunxiong , Huang Qingqing , Ma Yufei , Li Yuanfeng , Liu Yong , Liu Yang , Shi Linqi , Huang Fan 
Published: October 2024

AbstractTumor progression is associated with tumor‐cell softening. Improving the stiffness of the tumor cells can make them more vulnerable to lymphocyte‐mediated attack. Tumor cell membranes typically exhibit higher cholesterol levels than normal cells, making tumor cells soft. Herein, we demonstrate a mechanical immune checkpoint inhibitor (MICI) formulated by cyclodextrin (CD) lipids and fusogenic lipids. Through fusing CD lipids into the tumor cell membrane using a fusogenic liposome formulation, the cholesterol in the plasma membrane is reduced due to the specific host–guest interactions between CD lipid and cholesterol. As a result, tumor cells are stiffened, and the activation of lymphocytes (including NK and cytotoxic effector T cells) is improved when contacting the stiffened tumor cells, characterized by robust degranulation and effector cytokine production. Notably, this treatment has negligible influence on the infiltration and proliferation of lymphocytes in tumor tissues, confirming that the enhanced antitumor efficacy should result from activating a specific number of lymphocytes caused by direct regulation of the tumor cell stiffness. The combination of MICIs and clinical immunotherapies enhances the lymphocyte‐mediated antitumor effects in two tumor mouse models, including breast cancer and melanoma. Our research also reveals an unappreciated mechanical dimension to lymphocyte activation.
In silico and in vitro evaluation of a PE38 and Nb‐based recombinant immunotoxin targeting the GRP78 receptor in cancer cells
Authors: Khoshbakht Mona , Forghanifard Mohammad Mahdi , Aghamollaei Hossein , Amani Jafar 
Published: October 2024

Cancer is a global health problem despite the most developed therapeutic modalities. The delivery of specific therapeutic agents to a target increases the effectiveness of cancer treatment by reducing side effects and post‐treatment issues.Our aim in this study was to design a recombinant protein consisting of nanobody molecules and exotoxin that targets the surface GRP78 receptor on tumor cells. Bioinformatics methods make drug design and recombinant protein evaluation much easier before the laboratory steps.Two constructs were designed from a single‐variable domain on heavy chain nanobody domains and PE toxin domains II, Ib, and III. The physicochemical properties, secondary structure, and solubility of the chimeric protein were analyzed using different software. Prostate cancer DU‐145 and breast cancer MDA‐MB‐468 cell lines were used as GRP78‐positive and negative controls, respectively. Accordingly, the cytotoxicity, binding affinity, cell internalization, and apoptosis were evaluated using MTT, enzyme‐linked immunosorbent assay, and western blot. The results showed that in the DU‐145 cell line, the cytotoxicity of two recombinant immunotoxins is dose and time‐dependent. In MDA‐MB‐468 and HEK‐293 cells, such an event does not occur. It is possible that two constructs designed for immunotoxins can attach to GRP78‐positive cancer cells and then eradicate cancer cells by internalization and apoptosis. As our in vitro results were in line with in silico data confirming the Bioinformatics predictions, it can be concluded that the designed recombinant immunotoxins may exhibit therapeutic potential against GRP78‐positive tumor cells.
Vom Abriss zum Neubau: Die Hahnwaldbücke in Niedernhausen
Authors: Schölch Udo , Wetzel Timm , Ramolla Thomas , Keller Thorsten , Schmitz Andreas , Cemhan Sinan 
Published: October 2024

AbstractBei dem Ersatzneubau im Zuge der L 3027 handelt es sich um eine Straßenbrücke über elf Bahngleise im Ortskern von Niedernhausen mit einer Stützweite von 73 m. Die Planung erfolgte unter hohem Zeitdruck, da die Bestandsbrücke noch vor Erreichen der Restnutzungsdauer wegen Pfeilerschiefstellungen außer Betrieb genommen werden musste und ein Ersatz aus verkehrlichen Gründen dringlich war. Da die Sicherheitsanforderungen der Deutschen Bahn (DB) eine Änderung der Konstruktion erfordern, ist das neue Bauwerk als Stabbogenbrücke (mit obenliegendem Tragwerk) ausgebildet. Neben der Anpassung des Bauwerks an den Stand der Technik wurde auch ein Radfahrstreifen im Straßenquerschnitt integriert. Die Herstellung des Überbaus erfolgte aus transportablen Einzelteilen auf einem Montageplatz in etwa 600 m Entfernung oberhalb der Ortslage Niedernhausen. Im Frühjahr 2023 erfolgte der Transport der etwa 600 t schweren Stahlkonstruktion durch den Ort Niedernhausen und anschließend der Einschub über eine Zwischenstützung in die Endlage. Die Bauausführung ab dem Zeitpunkt des Abbruchs der Bestandsbrücke bis zum Einschub der neuen Stabbogenbrücke dauerte von September 2021 bis Juni 2023. Mit dem vorliegenden Bericht soll der Bogen ausgehend von den Herausforderungen des Erhaltungsmanagements für die Bestandsbrücke über die Planung des Ersatzneubaus bis zur Bauausführung und Verkehrsfreigabe gespannt werden.
Thermal Runaway of Na‐Ion Batteries with Na3V2O2(PO4)2F Cathodes
Authors: Zakharchenko Tatiana K. , Nikiforov Dmitriy I. , Serdyukov Georgiy D. , Komissarov Pavel V. , Shkuratov Mikhail O. , Dzuban Alexander V. , Lakienko Grigorii P. , Gordienko Yuriy A. , Yashina Lada V. , Itkis Daniil M. 
Published: October 2024

AbstractThe metal‐ion battery manufacturing growth rates increase attention to the safety issues. For promising sodium‐ion batteries, this topic has been studied in much less detail than for the lithium‐ion ones. Here, we explored the thermal runaway process of Na‐ion pouch cells with the Na3V2O2(PO4)2F (NVOPF)‐based cathode. The thermal runaway onset temperature for such cells is noticeably higher than that for the NMC‐based LIBs. We show that thermal runaway is triggered by the anode and the separator decomposition rather than by the processes at the cathode. The composition of the gas mixture released during thermal runaway process is similar to that for Li‐ion batteries. The results suggest that sodium‐ion batteries based on polyanionic cathodes can pave the way to safer metal‐ion energy storage technologies.
Flexible Micro‐Supercapacitors with Enhanced Energy Density Utilizing Flash Lamp Annealed Graphene‐Carbon Nanotube Composite Electrodes
Authors: Myung Yusik , Kim TaeYoung 
Published: October 2024

AbstractAs demand for micro‐power sources grows, micro‐supercapacitors (MSCs) have become critical for miniaturized devices, offering robust electrochemical energy storage. However, the challenge remains to develop a simple, scalable fabrication method that achieves both high energy and power densities. In this study, we present a refined approach to fabricating MSCs with 3D interconnected graphene/carbon nanotube (CNT) composite electrodes. Our method combines flash lamp annealing (FLA) and laser ablation, where FLA converts graphene oxide (GO) and CNT composite films into 3D‐structured graphene/CNT electrodes, and laser ablation precisely patterns them into interdigitated designs. This dual‐process technique produces MSCs with exceptional electrochemical performance, including an impressive areal capacitance of 26.11 mF/cm2 and a volumetric capacitance of 31.88 F/cm3. These devices also achieve energy densities of 3.72 μWh/cm2 and 4.43 mWh/cm3, maintaining 97 % of their initial capacitance under extreme bending, demonstrating outstanding mechanical flexibility and durability. Furthermore, the scalability of this method was validated by configuring MSCs in series and parallel, achieving enhanced voltage and current outputs without additional interconnections. Overall, the integration of FLA and laser ablation holds significant promise for advancing the performance and scalability of micro‐sized energy storage devices, addressing the growing need for efficient, flexible, and high‐capacity micro‐power sources.
Errichtung modularisierter Schalendächer mit vorgespannten Trockenfugen
Authors: Hofmann Felix , Hägle Marius , Stark Alexander 
Published: October 2024

AbstractDie in den letzten Jahrzehnten exponentiell angestiegene Betonproduktion hat einen hohen Rohstoffverbrauch und einen großen Anteil an den weltweiten CO2‐Emissionen zur Folge. Für einen schonenderen Ressourceneinsatz können materialeffiziente Strukturen wie Schalentragwerke, die an den Kraftverlauf angepasst sind, zugrunde gelegt werden. Aufgrund ihrer gekrümmten Geometrie ist die Herstellung von Schalentragwerken häufig aufwendig. Das modulare Bauen mit industriell vorproduzierten Betonbauteilen kann dabei einen Beitrag zu effizienteren Produktions‐ und Errichtungsprozessen leisten, sodass Vorteile der Vorfertigung mit den Vorteilen materialeffizienter Tragstrukturen kombiniert werden. In diesem Beitrag wird ein Konzept zur Modularisierung von einfach gekrümmten Schalentragwerken vorgestellt und eine Methode zur schnellen Errichtung gekrümmter Strukturen mit vorproduzierten einzelnen Fertigteilen und vorgespannten Trockenfugen aufgezeigt. Die Machbarkeit wird mit experimentellen Untersuchungen demonstriert.
Cost‐Effectiveness of Computer‐Assisted Cytology in a Primary hrHPV‐Based Cervical Cancer Screening Programme
Authors: Olthof Ellen M. G. , Kaljouw S. , van Kemenade Folkert J. , Uyterlinde Anne M. , de Kok Inge M. C. M. 
Published: October 2024

ABSTRACTBackgroundComputer‐assisted screening (CAS) shows equal performance compared to manual screening, although results are heterogeneous. Furthermore, using CAS may save costs through a potentially increased screening productivity of technicians, therefore also offering a solution for temporary and structural capacity shortage. We evaluated the circumstances under which CAS will be cost‐effective compared to manual cytology triage in a primary HPV‐based cervical screening programme.MethodsMicrosimulation model MISCAN‐Cervix was used to evaluate 198 different CAS scenarios with varying probabilities to detect cervical intraepithelial neoplasia grade 1 (CIN1) and CIN3 and cost reductions per test, compared to manual cytology triage. Cost‐effectiveness was evaluated by costs per (quality‐adjusted) life year ((QA)LY) gained.ResultsCAS will be cost‐effective in all scenarios, except for the following combinations: (1) no cost reduction and an increased probability of detecting CIN1, (2) a cost reduction of €2 per test and an increased probability of detecting CIN1 from 4% onwards or (3) a cost reduction of €4 per test and an increased probability of detecting CIN1 from 6% onwards, compared to manual cytology triage. All CAS scenarios with any reduction in the probability of detecting CIN1 (i.e., increased CIN2+ specificity), or a reduction in costs from €6 per test onwards suggested a more cost‐effective strategy compared to manual cytology triage.ConclusionAs we based our analysis on a realistic range in costs and test performance, the implementation of CAS is likely to be cost‐effective. Our results can be used as a guideline to advise when to choose CAS instead of manual cytology triage.
Which Moments Matter Most? Investigating Boundary Conditions of the Effect of Specific Moments on Overall Evaluations of Customer Experiences
Authors: Blečić Aleksandar , Kuester Sabine 
Published: October 2024

ABSTRACTCustomer experience (CE) often occurs as a temporal sequence of events that unfold over time. This research investigates the circumstances under which specific moments in the temporal sequence of a CE, such as the beginning or the end, have a disproportionate effect on customers' overall CE evaluations. Specifically, this research explores two boundary conditions of the effect of specific moments: incident valence and perceived control. The results of three scenario experiments, conducted with consumers in two contexts (hedonic and utilitarian), reveal that negative incidents at the end of a CE disproportionately influence overall CE evaluations across these different service contexts, demonstrating recency effects. However, these recency effects do not occur for positive incidents and are only present for individuals with heightened perceived control. Our findings address recent calls to further explore the role of timing and valence in CE evaluations and provide novel insights into the moderating role of perceived control on the effect of specific moments on overall CE evaluations. This research also offers practical guidance to help managers design more effective CEs.
Rotigaptide inhibits spontaneous contractions of gastric smooth muscle in diabetic rats via the PKCα‐Cx43 pathway
Authors: Changri Lu , Sun Haibei , Bao Yitegele , Zhang Mohan 
Published: October 2024

AbstractThe study aimed to investigate the effect of rotigaptide (ZP123) on spontaneous contractions of gastric smooth muscle in diabetic rats and explore the underlying mechanisms. Twelve rats were randomly divided into model and normal control groups. Changes in gastric smooth muscle spontaneous contractions in each group were observed. Western blot analysis was performed to detect Cx43 and PKCα expression. Rat gastric smooth muscle cells were cultured in vitro and divided into normal glucose, high glucose and high glucose+rotigaptide group. The intracellular Ca2+ content was observed by immunofluorescence. The amplitude and frequency of gastric smooth muscle spontaneous contractions were reduced in the model group than the normal control group (all p < .01), which were reduced after rotigatide treatment than before treatment in the model group (all p < .01). The model+rotigaptide group showed decreased membrane expression of Cx43, increased cytoplasmic expression of Cx43, increased membrane expression of p‐PKCα Thr497 and lower membrane/cytoplasm ratio of Cx43 expression compared with the model group (all p < .01). The intracellular Ca2+ content was increased in the high glucose group than the normal glucose group (p < .01), while no significant difference was observed between the high glucose+rotigaptide and high glucose groups. Our findings suggest that rotigatide can stabilize the intracellular Ca2+ concentration in gastric smooth muscle cells under high glucose condition by upregulating PKCα activity and downregulating the number of GJs and the opening rate of GJ hemichannels through the PKCα‐Cx43 pathway, thus inhibiting spontaneous contractions of gastric smooth muscle in diabetic rats.
Photoinduced Self‐assembly: An Alternative Strategy for the Construction of Coordination Oligomers and Polymers
Authors: Honda Takuma , Hirake Takumi , Kondo Mio , Masaoka Shigeyuki , Fujimori Keiichi , Moriuchi‐Kawakami Takayo , Hirahara Masanari 
Published: October 2024

AbstractSelf‐assembled oligonuclear and polynuclear complexes have numerous functionalities and potential applications. Generally, such compounds have been constructed by thermal substitution reactions with bridging ligands. Herein, we report bottom‐up and photochemical construction of functional coordination oligomers and polymers by photosubstitution‐induced self‐assembly. The photosubstitution reactions of a ruthenium precursor complex with bridging ligands having pyrazole moieties afford mono‐, di‐, tri‐, tetra‐, and pentanuclear ruthenium complexes, Ru1–Ru5, which have one‐dimensional architectures. Intramolecular hydrogen bonding between each bridging ligand is a key to construct the molecular nanowires. All the complexes have been isolated and thoroughly characterized. The photochemically synthesized ruthenium complexes act as synthons for longer metal‐complex‐based nanowires with a length of the order of tens‐of nanometers. The multinuclear complexes are generated by photoinduced self‐assembly in the presence of a base, and they undergo photoinduced disassembly in the presence of acid.
Endogenous Cu(II) Labeling for Distance Measurements on Proteins by EPR
Authors: Hunter Hannah R. , Kankati Shashank , Hasanbasri Zikri , Saxena Sunil 
Published: October 2024

AbstractIn‐cell measurements of the relationship between structure and dynamics to protein function is at the forefront of biophysics. Recently, developments in EPR methodology have demonstrated the sensitivity and power of this method to measure structural constraints in‐cell. However, the need to spin label proteins ex‐situ or use noncanonical amino acids to achieve endogenous labeling remains a bottleneck. In this work we expand the methodology to endogenously spin label proteins with Cu(II) spin labels and describe how to assess in‐cell spin labeling. We quantify the amount of Cu(II)‐NTA in cells, assess spin labeling, and account for orientational effects during distance measurements. We compare the efficacy of using heat‐shock and hypotonic swelling to deliver spin label, showing that hypotonic swelling is a facile and reproducible method to efficiently deliver Cu(II)‐NTA into E. coli. Notably, over six repeats we accomplish a bulk average of 57 μM spin labeled sites, surpassing existing endogenous labeling methods. The results of this work open the door for endogenous spin labeling that is easily accessible to the broader biophysical community.