bluuebunny/crossref_metadata_2025_split huggingface dataset:
Two Approaches to the Synthesis of Redox‐Switchable 5,10,20‐Triaryl‐5,15‐diazaporphyrinoids
Authors: Murata Yui , Sudoh Keisuke , Furukawa Ko , Nakano Haruyuki , Matano Yoshihiro 
Published: November 2024

AbstractDespite the significant development and extensive application of phthalocyanine and related azaporphyrins, little attention has been paid to meso‐N‐substituted azaporphyrinoids. Here, we report new derivatives of 5,10,20‐triaryl‐5,15‐diazaporphyrinoids (Ar3DAP), which are reversibly redox‐switchable between the 18π‐ and 19π‐electron state. Four kinds of metal(II) complexes and free bases of Ar3DAP were prepared by metal‐templated cyclization of metal(II) complexes of 5,10,15‐triaryl‐10‐azabiladiene‐ac with sodium azide or copper‐catalyzed N‐phenylation of 10,20‐diaryl‐5,15‐diazaporphyrins (Ar2DAP) with diphenyliodonium hexafluorophosphate. In particular, regioselective N‐phenylation of covalently linked Ar2DAP dimer afforded two kinds of dimers bearing one or two meso‐N‐phenyl groups. Cyclic voltammetry revealed that attaching one aryl group onto the meso‐nitrogen atom markedly changed the redox potentials of the DAP ring. The aromaticity and optical properties of the new Ar3DAP π‐electron systems were assessed using various spectroscopic measurements and density functional theory calculations. The distribution pattern of an electron spin in the neutral Ar2DAP–Ar3DAP radical revealed that the meso‐N‐phenyl group had a remarkable effect on spin delocalization of DAP π‐radical. The present study provides valuable information for understanding the effects of the number of meso‐N‐substituents on azaporphyrin‐based π‐electron systems.
Impact of organisational capabilities on the implementation of circularity‐oriented activities
Authors: Dagilienė Lina , Varaniūtė Viktorija , Šutienė Kristina 
Published: November 2024

AbstractA transition to a circular economy should be seen as a fundamental systemic change involving a rethinking and development of organisational capabilities. Most studies have focused on the normative aspects of what circular capabilities and circularity‐oriented activities should be. There is a lack of research empirically demonstrating what dynamic capabilities influence circularity‐oriented activities, which range from product design to waste management. By using survey data of 139 incumbent manufacturing companies, this paper investigates organisational capabilities that influence the implementation of circularity‐oriented activities. The functional relationship analysis is performed by combining a variance‐based structural equation model with ordered logistic regression. Zooming‐in and zooming‐out perspectives highlight the dynamic nature of circular capabilities. Our empirical results show that zooming‐out capabilities (adaptability to the network, adaptability to regulation, consumer acceptance) positively influence product design, while zooming‐in capabilities (financial capabilities and organisational resources and skills) positively affect circularity‐oriented activities, such as cleaner production and waste management.
The Structural Permissiveness of Triosephosphate Isomerase (TpiA) of Escherichia coli
Authors: Calles Belén , Pitarch Borja , de Lorenzo Víctor 
Published: November 2024

AbstractTriosephosphate isomerase (TpiA) is widely regarded as an example of an optimally evolved enzyme due to its essential role in biological systems, its structural conservation, and its near‐perfect kinetic parameters. In this study, we investigated the structural robustness of the archetypal TpiA variant from Escherichia coli using an in vitro 5‐amino acid linker scanning method. The resulting library was introduced into a tpiA mutant strain for functional complementation. From this library, 16 TpiA variants that were phenotypically indistinguishable from the wild‐type enzyme were selected for further analysis. Although all variants retained enzymatic activities within the wild‐type range, several insertions were found in highly structured protein domains where the linker was expected to cause significant structural perturbations. Despite these potentially disruptive additions, the enzymes maintained their activity even when expressed in a dnaK mutant, suggesting that chaperones did not compensate for structural abnormalities in vivo. Additionally, when these mutant TpiA variants were produced using an in vitro transcription/translation system, they exhibited enzymatic activity comparable to, and in some cases exceeding, that of the non‐mutated enzyme. AlphaFold2 exposed that insertions reconstructed the local architecture of the nearby amino acid sequences. The evolutionary implications of this remarkable structural resilience are discussed.
A Facile Label‐Free Colorimetric Assay for DNase I Activity Based on the Peroxidase‐Like Activity of Functional Nucleic Acids
Authors: Song Yi , Yan Xu‐Xia , Sun Shao‐Yu , Bian Wei‐Jie , Su Xiao‐Dong , Qiu Hui‐Dong , Zhou Qian‐Yu 
Published: November 2024

AbstractDNase I plays a crucial role in fundamental biological processes, including gene expression, DNA repair, and apoptosis. Therefore, it is important to develop a simple and efficient method to detect DNase I activity. In this work, a colorimetric assay based on functional nucleic acid for sensitive DNase I detection was reported. The functional nucleic acids with G‐rich bases exhibit peroxidase‐like activity under acetic acid conditions, capable of catalyzing the oxidation of chromogenic substrate 3,3′,5,5′‐tetramethylbenzidine (TMB). The specific nucleic acid is designed as the substrate for DNase I, which can hydrolyze the strand and reduce the catalytic activity of the reaction system. Based on this, a sensitive, simple, efficient, and cost‐effective colorimetric detection platform was constructed for the quantitative analysis of DNase I. The detection limit (3σ/s) for DNase I was 0.046 U/mL with a linear range of 0.1–1 U/mL. Moreover, the practicality of this colorimetric detection platform was demonstrated by detecting DNase I in human serum.
Compartmentalized Sesquiterpenoid Biosynthesis and Functionalization in the Chlamydomonas reinhardtii Plastid
Authors: Gutiérrez Sergio , Overmans Sebastian , Wellman Gordon B. , Lauersen Kyle J. 
Published: November 2024

AbstractTerpenoids play key roles in cellular metabolism and can have specialized functions. Their heterologous production in microbial hosts offers an alternative to natural extraction. Here, we developed a subcellular engineering approach in the model green alga Chlamydomonas reinhardtii by targeting both sesquiterpenoid synthases and cytochrome P450s (CYPs) to the plastid, exploiting its photosynthetic electron transport chain to drive CYP‐mediated oxidation without reductase partners. Nuclear‐encoded sesquiterpenoid synthases were expressed with farnesyl pyrophosphate synthase fusions and targeted to the plastid, while CYPs were modified for soluble localization in the plastid stroma by removing transmembrane domains. The plastid environment supported hydroxylation, epoxidation, and oxidation reactions, with functionalization efficiencies reaching 80 % of accumulated products. Carbon source availability influenced product ratios, revealing metabolic flexibility in the engineered pathways. Overall sesquiterpenoid yields ranged between 250–2500 μg L−1 under screening conditions, establishing proof‐of‐concept for using plastid biochemistry in complex terpenoid biosynthesis. Living two‐phase terpenoid extractions with different perfluorinated solvents revealed variable performances based on sesquiterpenoid functionalization and solvent type. This work demonstrates that photosynthetic electron transport can drive CYP‐mediated functionalization in engineered subcellular compartments. However, improvements in photobioreactor cultivation concepts will be required to facilitate the use of algal chassis for scaled production.
Catalytic Activity of Cellulose‐Supported Platinum and Palladium Nanoparticles for Allylbenzene Hydrogenation
Authors: Thiel Tabea Angela , Parapat Riny Yolandha , Schroeter Michael , Schwarze Michael 
Published: November 2024

AbstractPlatinum and palladium nanoparticles were successfully deposited on tunicate cellulose via the photodeposition or microemulsion deposition method. Evenly distributed, small and narrow‐sized particles in the range of 2–3 nm were obtained for microemulsion‐prepared cellulose catalysts. The photodeposition method led to larger particle sizes, broader size distribution, and occasional agglomerations. The catalysts were tested in the allylbenzene hydrogenation reaction at room temperature and the results were compared to commercially available catalysts. Because of smaller particles, both microemulsion‐prepared catalysts and photodeposited ones show better activity than commercial catalysts. Even platinum and palladium nanoparticles were active for the hydrogenation, only cellulose‐supported platinum nanoparticles showed good stability. For palladium nanoparticles, stronger leaching from the surface of cellulose was observed. Cellulose‐supported catalysts were recycled, and reusability is comparable to commercial catalysts. Therefore, cellulose could be used as an alternative catalyst support.
Exploring Glycan‐Lectin Interactions in Natural‐Like Environments: A View Using NMR Experiments Inside Cell and on Cell Surface
Authors: Bertuzzi Sara , Lete Marta G. , Franconetti Antonio , Diercks Tammo , Delgado Sandra , Oyenarte Iker , Moure Maria J. , Nuñez‐Franco Reyes , Valverde Pablo , Lenza Maria Pia , Sobczak Klaudia , Jiménez‐Osés Gonzalo , Paulson James C. , Ardá Ana , Ereño‐Orbea June , Jiménez‐Barbero Jesús 
Published: November 2024

AbstractGlycan‐mediated molecular recognition events are essential for life. NMR is widely used to monitor glycan binding to lectins in solution using isolated glycans and lectins. In this context, we herein explore diverse NMR methodologies, from both the receptor and ligand perspectives, to monitor glycan‐lectin interactions under experimental conditions mimicking the native milieu inside cells and on cell surface. For the NMR experiments inside cells, galectin‐7 is employed as model, since most galectins are soluble and carry out their functions in the cellular micro‐environment. Using Danio Rerio oocytes, the 1H‐15N HMQC NMR spectrum of a folded galectin has been observed inside cell for the first time, using a glycomimetic ligand (TDG) to overcoming the natural tendency of galectins to bind to numerous galactose‐containing receptors within cells. Alternatively, most lectins, other than galectins, are displayed on the cell surface, providing a multivalent presentation to bind their glycan partners in cis (at the same cell) or in trans (on other cells). In this case, ligand‐based STD‐NMR experiments have been successfully applied to account for the interactions of natural glycans and glycomimetics with Siglec‐10. These methodologies provide the proof‐of‐concept to open the door to the NMR analysis of the recognition of glycans in native‐like settings.
Intermolecular Forces‐Oriented Growth of MOF‐on‐MOF Heterostructures
Authors: Chen Jiaxin , Hang Xinxin , Du Meng , Yang Zhangbin , Li Runtao , An Yang , Pang Huan 
Published: November 2024

AbstractWell‐controlled conjugation of distinct metal‐organic frameworks (MOFs) with dissimilar components and structures into a multi‐component MOF system is important for the design of myriad materials with structural complexity, integrated properties, and desired applications. Herein, we developed an interesting integration strategy that relies on intermolecular force, and which can overcome the difference in lattice parameters. The strategy uses the pre‐formed MOF matrixes as seeds to direct the self‐assembly of secondary MOF particles for the construction of hybrid MOFs. As a proof of concept, the representative core‐satellite‐type Ni‐MOF@ZIF‐8 and core‐shell‐type MOF‐74@ZIF‐8 heterostructures were achieved. Theory calculations elucidate the uncommon formation of well‐defined hybrid MOFs by self‐assembly of secondary ZIF‐8 particles to anchor on Ni‐MOF or MOF‐74 seed surface via hydrogen bonds and van der Waals interactions. We anticipate that this work opens an avenue to design the multi‐component MOF systems from different MOFs with lattice mismatching.
Triskelion‐Shaped Hexabenzocoronenes: Synthesis and Characterization of Tris‐Substituted HBC Derivatives
Authors: Buck Janina , Hampel Frank , Hirsch Andreas 
Published: November 2024

AbstractThe synthesis of unprecedented triskelion‐shaped hexa‐peri‐hexabenzocoronenes with C3, C3h or D3h symmertry is reported. We present a new, five step synthetic access to tris‐iodinated HBC derivatives carrying different solubilizing moieties (tert‐butyl and mesityl), which serve as suitable building blocks for further functionalization. These molecules can undergo Sonogashira cross coupling reactions to obtain a series of seven ethynyl tris‐substituted HBCs. The coupling partners range from carbon‐based aromatic scaffolds (tBu‐benzene, naphthalene, phenanthrene) to ligands for metal complexes (bipyridine, phenanthroline, terpyridine, acetylacetone). The optoelectronic properties were investigated by UV/vis absorption spectroscopy resulting in a significant bathochromic shift of the absorption maximum compared to the iodinated starting material. Semiempirical calculations were used to determine the conformation and symmetry of the compounds.
Twofold 6π‐Electrocyclization as a Route Toward Multi‐Heteroatom‐Doped Nanographenes Built on a 1,4‐Dihydropyrrolo[3,2‐b]pyrrole Core
Authors: Górski Krzysztof , Pejov Ljupcho , Jørgensen Kåre B. , Knysh Iryna , Jacquemin Denis , Gryko Daniel T. 
Published: November 2024

AbstractHere we present a highly versatile synthetic strategy based on twofold 6π‐electrocyclization accompanied with HBr elimination as a novel approach towards centrosymmetric multi‐heteroatom‐doped nanographenes build around an electron‐rich 1,4‐dihydropyrrolo[3,2‐b]pyrrole core. A straightforward synthesis from readily available substrates offers a unique possibility of fusing the 1,4‐dihydropyrrolo[3,2‐b]pyrrole subunit not only with carbocyclic building blocks, such as electron‐deficient phenanthrenes, chrysenes, or [4]helicenes, but also with heterocyclic systems, such as benzo[b]furan and 5‐thiatruxene. The clear advantage of this strategy is that there is no requirement to assemble complex scaffolds possessing bromoaryl units since bromine atom is introduced by bromination of 1,4‐dihydropyrrolo[3,2‐b]pyrrole core which, because of its exceptionally electron‐rich character, is straightforward reaction. The obtained χ‐shaped and S‐shaped nanographenes containing 10 or more fused rings, exhibit visible‐range emissions characterized by fluorescence quantum yields reaching 48 %. Computational studies of the reaction mechanism revealed that the 6π‐electrocyclization is kinetically favourable over photo‐induced direct arylation. Steady‐state UV/Visible spectroscopy reveals that upon photoexcitation, the prepared S‐shaped N‐doped nanographenes undergo mostly radiative relaxation leading to large fluorescence quantum yields. We anticipate that this chemistry will empower the creation of new materials with various functionalities.
Electrochemical and Thermal Evolution of P2 Na2/3MnO2
Authors: Thilakarathna B. D. K. K. , Mittal Uttam , Peng Jian , Brocklebank Daniel , Brand Helen E. A. , Sharma Neeraj 
Published: November 2024

AbstractP2 Na2/3MnO2 can be used as a cathode material in sodium‐ion batteries. Here, the electrochemical‐temperature‐dependent evolution of P2 Na2/3MnO2 is investigated using X‐ray powder diffraction. P2 Na2/3MnO2 powder under a N2 atmosphere shows evidence of the formation of a monoclinic C2/m phase, from about 450 °C. The P2 Na2/3MnO2 electrode sealed in a capillary undergoes a sequence of phase transitions from the as‐prepared hexagonal P63/mmc to a secondary hexagonal P63/mmc phase followed by a transition to Mn3O4 and subsequently MnO. NaF also appears parallel to the formation of the secondary hexagonal phase. These transitions suggest a local reducing environment as the Mn oxidation state evolves from 3+/4+ to 2+. The samples at various states of charge show similar thermal evolution with the exception of the discharged (Na‐inserted) state which features a slightly more complex evolution. Understanding the structure and thermal evolution at various states of charge and under various conditions provides insight into the stability of these potential cathode materials.
Human Pancreas‐Derived Organoids with Controlled Polarity: Detailed Protocols and Experimental Timeline
Authors: Kiss Aletta , Farkas Attila , Ayaydin Ferhan , Lázár György , Varga Árpád , Maléth József 
Published: November 2024

AbstractSince their discovery, 3D cell cultures have emerged as powerful tools across various basic, translational research, and industrial discovery projects. One such application is in the physiological and pathophysiological modeling of pancreatic exocrine functions, which addresses critical clinical challenges, including acute and chronic pancreatitis. While several methods now exist for generating epithelial organoids (derived from induced pluripotent, embryonic, or adult stem cells), the advent of patient‐derived organoids (PDOs) with controlled polarity has introduced a new frontier in pancreatic research. This advancement has significantly expanded the methodological arsenal available for studying human pancreatic epithelial secretion.In this article, we present basic protocols and a troubleshooting guide for an advanced culture method that results in an apical‐to‐basal polarity switch. Alongside the protocols, we emphasize a comprehensive cost breakdown, an aspect often challenging to estimate when implementing new techniques. By sharing the technical nuances and financial implications of these protocols, we aim to encourage researchers to transition from rodent models to primary human epithelial cells wherever feasible. This aligns with the U.S. Environmental Protection Agency's efforts to accelerate the translation of significant scientific findings to address major clinical needs. © 2024 Wiley Periodicals LLC.Basic Protocol 1: Establishment and maintenance of pancreatic PDOsBasic Protocol 2: Cryopreservation and thawing of pancreatic PDOsBasic Protocol 3: Inducing polarity switching in pancreatic PDOs
Active restoration efforts drive community succession and assembly in a desert during the past 53 years
Authors: Hou Qingqing , Hu Weigang , Sun Ying , Morriën Elly , Yang Qiang , Aqeel Muhammad , Du Qiajun , Xiong Junlan , Dong Longwei , Yao Shuran , Peng Jie , Sun Yuan , Akram Muhammad Adnan , Xia Rui , Zhang Yahui , Wang Xiaoting , Xie Shubin , Wang Liang , Zhang Liang , Li Fan , Deng Yan , Luo Jiali , Yuan Jingyan , Ma Quanlin , Niklas Karl J. , Ran Jinzhi , Deng Jianming 
Published: November 2024

AbstractRegreening efforts in deserts have been implemented globally to combat land degradation and desert expansion, but how they affect above‐ and belowground community succession and assembly processes remains unknown. Here, we examined variations in plant and soil microbial community attributes along a 53‐year restoration chronosequence following the establishment of straw checkerboard barriers (SCBs) in the Tengger Desert of China. This approach is a combination of fixing shifting sand and adding organic material (straw) simultaneously to expedite vegetation restoration by enhancing the success of plant establishment. Our findings revealed that the establishment of SCBs significantly triggered plant and soil microbial communities to gradually approximate those of the natural community along restoration duration. We observed positive and negative bidirectional shifts in plant and soil microbial community composition. Critical temporal threshold zones for relatively rapid changes in community composition were identified, with 2–15.5 years for plants, 0.5–8.5 years for bacteria, and 2–8.5 years for fungi. This suggests a delayed response of plant communities to restoration efforts compared with soil microbial communities. Both stochastic and deterministic processes regulated plant and soil microbial community assembly. Stochastic processes played a more important role in plant and fungal community succession, whereas deterministic processes primarily governed bacterial succession. In terms of deterministic processes, temporal variations in community composition mainly resulted from the intrinsic correlations among plant, bacterial, and fungal communities, as well as an increase in soil organic carbon (SOC) with restoration duration. Thus, temporal patterns and functional contributions of bacterial communities appear to be more predictable than those of plant and fungal communities during desert ecosystem restoration. This study emphasizes that plant‐bacteria‐fungi correlations and increasing SOC content are critical for accelerating community succession and promoting dryland restoration. Future studies should explore and integrate temporal variations and restoration effects of multiple ecosystem functions to better predict dryland development and resilience to global climate changes over a large temporal scale.
Effect of Pomacea canaliculata on Limnodrilus hoffmeisteri: Behavior, Oxidative Stress, and Microbiota Alterations
Authors: Liu Mingyuan , Sui Changrun , Wang Baolong , Ma Pengfei , Zhang Weixiao , Huang Ruipin , Wang Yuqing , Qiu Zhujun , Zhao Wenyu , Zhang Tao , Zhang Qian , Liu Ying 
Published: November 2024

ABSTRACTPomacea canaliculata is an invasive species which has significantly impacted native ecosystems globally. The benthic worm Limnodrilus hoffmeisteri is essential for the stability of the native aquatic ecosystem, facilitating the nutrient cycle dynamics through bioturbation. Nevertheless, limited information exists regarding the impact of P. canaliculata on those key native benthic species. Present study evaluated the impacts of P. canaliculata on L. hoffmeisteri by exposing L. hoffmeisteri to P. canaliculata (PC group) and the native snail Bellamya aeruginosa (BA group), with a control group consisting of no snails (NS group). The survival rate of L. hoffmeisteri in the PC group persisted diminished over 14 days, with notable declines in the rates of successful food acquisition and aggregation, an increase in migration, and a decrease in swing frequency. Elevated oxidative stress levels were linked to these alterations in L. hoffmeisteri behavior. Additionally, the presence of P. canaliculata increased the abundance of intestinal pathogenic bacteria in L. hoffmeisteri, with Aeromonas being one of the most lethal. Experimental models of Aeromonas‐free P. canaliculata (AFPC), re‐infected AFPC (IPC), and Aeromonas (As) were established to illustrate the role of Aeromonas in the decline of L. hoffmeisteri. Similar patterns in L. hoffmeisteri survival, behavior, and oxidative stress were observed in As, IPC, and PC group; however, these effects were mitigated by the elimination of Aeromonas in the AFPC group. Furthermore, L. hoffmeisteri was fatally affected by the four Aeromonas strains that were obtained from P. canaliculata intestine. These findings indicate that P. canaliculata exerts a deleterious impact on L. hoffmeisteri, and Aeromonas colonizing in intestine plays an important role. This study reveals a novel invasion mechanism of P. canaliculata.