bluuebunny/crossref_metadata_2025_split huggingface dataset:
High H2 permeability in F‐doped BaZr0.7Ce0.2Y0.1O3−δ perovskite membranes via thermodynamic controlled sintering
Authors: Gu Zhenbin , Tan Jinkun , Zhou Haoli , Liu Zhengkun , Ge Lin , Zhang Guangru , Jin Wanqin 
Published: November 2024

AbstractA raw hydrogen mixture frequently results in a reduction in conversion efficiency and the generation of undesired by‐products. The application of advanced membrane technology has the potential to offer an economically viable solution for the recovery of hydrogen from such mixtures. BaZr1−x−yCexYyO3−δ is increasingly regarded as an optimal perovskite hydrogen permeable membrane. Nevertheless, the main drawback to its use in a larger scale is the extremely low hydrogen permeability and stability. An original perovskite material is proposed in this study, BaZr0.7Ce0.2Y0.1O3−δ‐Fx. A thermodynamic‐controlled sintering strategy (TCS) has been employed to inhibit the evaporation of metals from ceramic solids. The TCS directly caused the hydrogen permeation flux to reach 1.07 ml·min−1 cm−2, representing a fourfold improvement. Furthermore, F‐doping demonstrated enhanced performance at low and medium temperatures. The aforementioned successful strategy provides an effective path for the tailoring of perovskite materials and promotes its application for the industrial‐scale separation of hydrogen.
Stabilisierung eines Strontiumhydridkomplexes mit einem Einzähnigen Carbazolylliganden und Dessen Reaktivität
Authors: Winkler Lucas , Hinz Alexander 
Published: November 2024

AbstractDer Strontiumhydridkomplex 2 [(dtbpCbz)SrH(L)]2 (L=Benzol, Toluol) wurde isoliert und konnte durch einen sterisch anspruchsvollen Carbazolylliganden (dtbpCbz=1,8‐bis(3,5‐ditertbutylphenyl)‐3,6‐ditertbutylcarbazolyl) stabilisiert werden. Verbindung 2 wurde durch Reaktion des Amids (dtbpCbz)SrN(SiMe3)2 mit Phenysilan dargestellt und durch 1H NMR‐Spektroskopie, Einkristallröntgenstrukturanalyse und schwingungsspektroskopische Methoden charakterisiert. Wir untersuchten die Reaktivität von 2 gegenüber Kohlenstoffmonoxid, Azobenzol sowie Trimethylsilylacetylen, wobei sich drei verschiedene Reaktivitätsarten zeigten: Addition, Reduktion und Deprotonierung. Die Reaktion von 2 mit Kohlenstoffmonoxid lieferte den Ethendiolat‐Komplex 4 durch Addition an die C−O Bindung, wohingegen bei der Umsetzung mit Azobenzol die Reduktion der N−N Doppelbindung sowie Eliminierung von Wasserstoff beobachtet wurde, welche zu einem heteroleptischen Strontiumkomplex mit einem radikalischen Azobenzenylliganden führte (5). Das terminale Alkin wird durch das Hydrid deprotoniert, wodurch der Acetylidkomplex 6 entstand.
A Chemically Powered Rotary Molecular Motor Based on Reversible Oxazepine Formation
Authors: Han Tian‐Jiao , Ke Xin‐Yan , Wang Min‐Can , Ni Shao‐Fei , Mei Guang‐Jian 
Published: November 2024

AbstractWhile biological machines are powered mainly by chemical transformations, chemically driven artificial rotary motor systems are very limited. Here, we report an aniline‐phenol‐based rotary molecular motor that operates via an information ratchet mechanism. The 360° directional rotation about a single covalent bond can be chemically driven by reversible oxazepine formation. Both the oxazepine formation and hydrolysis steps are kinetically gated via dynamic kinetic resolution, arising from the kinetic bias of chiral catalysts for enantiomers. Given the 95 % ee (97.5 : 2.5) and 88 % ee (94 : 6) of the individual gating steps of motor analogues, the overall directionality ratio could be calculated to be 91.7 : 8.3 (97.5 %×94 %≈91.7 %), which means that the motor will make one mistake (backward rotation) approximately every 11 to 12 turns.
Structural and Functional Characterization of an Amidase Targeting a Polyurethane for Sustainable Recycling
Authors: Rotilio Laura , Bayer Thomas , Meinert Hannes , Teixeira Luis M. C. , Johansen Martin B. , Sommerfeldt Andreas , Petersen Allan R. , Sandahl Alexander , Keller Malene B. , Holck Jesper , Paiva Pedro , Otzen Daniel E. , Bornscheuer Uwe T. , Wei Ren , Fernandes Pedro A. , Ramos Maria J. , Westh Peter , Morth J. Preben 
Published: November 2024

AbstractGlobal plastic production exceeded 400 million tons in 2022, urgently demanding improved waste management and recycling strategies for a circular plastic economy. While the enzymatic hydrolysis of polyethylene terephthalate (PET) has become feasible on industrial scales, efficient enzymes targeting other hydrolyzable plastic types, such as polyurethanes (PURs), are lacking. Recently, enzymes of the amidase signature (AS) family, capable of cleaving urethane bonds in a polyether‐PUR analog and a linear polyester‐PUR, have been identified. Herein, we present high‐resolution crystal structures of the AS enzyme UMG‐SP3 in three states: ligand‐free, bound with a suicidal inhibitor mimicking the transition state, and bound with a monomeric PUR degradation product. Besides revealing the conserved core and catalytic triad akin to other AS family members, the UMG‐SP3 structures show remarkable flexibility of loop regions. Particularly, Arg209 in loop 3 adopts two induced‐fit conformations upon ligand binding. Through structure‐guided kinetic studies and enzyme engineering, we mapped structural key elements that determine the enhanced hydrolysis of urethane and amide bonds in various small molecules, including a linear PUR fragment analog. Our findings contribute critical insights into urethanase activity, aiding PUR degradation campaigns and sustainable plastic recycling efforts in the future.
Bridged Carbolong Modulating Interfacial Charge Transfer Enhancement for High‐Performance Inverted Perovskite Solar Cells
Authors: Yang Yang , Chen Shiyan , Dai Zhiyuan , Wei Hang , Wan Shuyuan , Chen Yan , Sun Jinhan , Liu Zhe , Ding Liming , Xia Haiping , Chen Ruihao , Wang Hongqiang 
Published: November 2024

AbstractEfficient regulation of perovskite/C60 interface is crucial to improving the long‐term stability of the inverted perovskite solar cells (PSCs). However, precise methods for controlling the perovskite/C60 interface have yet to be thoroughly explored. Herein, we develop a carbolong chemical manipulation strategy to improve the interface contact of perovskite/C60 due to versatile functional groups and excellent optoelectronic properties of carbolong metallaaromatics. And constructing an electron‐transfer bridge enhances the interfacial interaction and accelerates interfacial electron transfer. The carbolong manipulation results in optimized energy level alignment, suppressed nonradiative recombination, and improved electronic contact. An impressive efficiency of 25.80% is demonstrated, with open‐circuit voltage and fill factor of 1.19 V and 84.53 %, respectively. The unsealed devices retain more than 98 % of their original efficiency after 1400 h of maximum power point tracking under illumination and demonstrate remarkable thermal stability, maintaining 93 % of their initial efficiency after 2500 h at 85 °C in a nitrogen atmosphere. And the encapsulated carbolong‐modified module achieved a high efficiency of 20.72 % (active area of 25.25 cm2) with robust operation stability.
Better Together: Photoredox/Copper Dual Catalysis in Atom Transfer Radical Polymerization
Authors: Sobieski Julian , Gorczyński Adam , Jazani Arman Moini , Yilmaz Gorkem , Matyjaszewski Krzysztof 
Published: November 2024

AbstractPhotomediated Atom Transfer Radical Polymerization (photoATRP) is an activator regeneration method, which allows for the controlled synthesis of well‐defined polymers via light irradiation. Traditional photoATRP is often limited by the need for high‐energy ultraviolet or violet light. These could negatively affect the control and selectivity of the polymerization, promote side reactions, and may not be applicable to biologically relevant systems. This drawback can be circumvented by an introduction of the catalytic amount of photocatalysts, which absorb visible and/or NIR light and, therefore, controlled, regenerative ATRP can be performed with the dual‐catalytic cycle. Herein, a critical summary of recent developments in the field of dual‐catalysis concerning Cu‐catalyzed ATRP is provided. Contributions of involved species are examined mechanistically, followed by challenges and future directions towards the next generation of advanced functional macromolecular materials.
Single‐Cell Secretome Profiling Enabled by Selective Enrichment and NanoLC‐MS/MS Analysis
Authors: He Yingyun , Liu Xinxin , Zhu Fengjiao , Dai Zhongpeng , Li Xiao , Li Linmei , Zhao Baofeng , Yuan Huiming , Lu Yao , Liang Zhen , Zhang Yukui , Zhang Lihua 
Published: November 2024

AbstractRecent advances in single‐cell proteomics enable the direct profiling of thousands of proteins from a single mammalian cell. However, due to the bottlenecks in detecting low‐abundance secreted proteins and extracellular vesicle (EV) proteins (collectively referred to as the secretome) against a background of high‐abundance proteins in serum‐containing culture medium, the comprehensive investigation of the secretome at the single‐cell level using nanoLC‐MS/MS still remains challenging. Herein, we report a novel single‐cell secretome profiling (SCSP) method by integrating the metabolic labeling of newly synthesized proteins, click chemistry‐based enrichment, and in situ digestion of the labeled secretome in an alkyne‐functionalized capillary micro‐reactor, followed by nanoLC‐MS/MS analysis. By this method, an average of 389 protein groups were quantified from the secretome of single HeLa cells (n=17), with a total of 752 protein groups confidently identified in the single‐cell secretome, which is a significant increase compared to the previously reported targeted analysis limited to dozens of secreted proteins by antibody recognition. These results indicated that our developed SCSP method would provide a powerful tool to gain insights into secretion heterogeneity and intercellular communication at the single‐cell level.
Stabilisation of a Strontium Hydride with a Monodentate Carbazolyl Ligand and its Reactivity
Authors: Winkler Lucas , Hinz Alexander 
Published: November 2024

AbstractThe molecular strontium hydride 2 [(dtbpCbz)SrH(L)]2 (L=benzene, toluene) was isolated and stabilized by employing a sterically demanding carbazole ligand (dtbpCbz=1,8‐bis(3,5‐ditertbutylphenyl)‐3,6‐ditertbutylcarbazolyl). Compound 2 was synthesized via phenylsilane metathesis with the corresponding amide (dtbpCbz)SrN(SiMe3)2 and characterized by 1H NMR, XRD and vibrational spectroscopy methods. We further investigated the stoichiometric reactivity of 2 towards carbon monoxide, azobenzene and trimethylsilylacetylene, showing three distinct reactivity pathways: addition, reduction and deprotonation. The reaction of 2 with carbon monoxide yields the ethenediolate complex 4 via addition, while with azobenzene reduction of the N−N double bond and release of hydrogen were observed, affording a heteroleptic strontium complex with a radical azobenzenyl ligand (5). The terminal alkyne is deprotonated by the hydride moiety to give the acetylide complex 6.
Functional Characterization and Molecular Basis of a Multi‐Site Halogenase in Naphthacemycin Biosynthesis
Authors: Hu Yu , Peng Shu‐Ya , Ma Xueyang , Chen Hongwei , Nie Qiu‐Yue , He Jun‐Bin , Chen Qianqian , Zhou Qiang , Lu Xin‐Hua , Hua Qiang , Yang Donghui , Liang Yong , Ma Ming , Tang Gong‐Li 
Published: November 2024

AbstractHalogenases are spurring a growing interest in the fields of biosynthesis and biocatalysis. Although various halogenases have been identified in numerous natural product biosynthetic pathways, the mechanisms for multiple halogenations and site‐selectivity remain largely unclear. In this study, we biochemically characterized FasV, a flavin‐dependent halogenase (FDH) that catalyzes five successive chlorinations in the biosynthesis of the naphthacene‐containing aromatic polyketide naphthacemycin. This multiple halogenation reaction was elucidated to occur in an orderly fashion, as evidenced by enzyme kinetics, time‐course assays, and computational simulations. Crystallographic analyses and mutagenesis studies revealed previously unrecognized amino acid residues, including T53, L81, F93, and I212, that are crucial for controlling regioselectivity and substrate specificity. Based on this, a I212T mutant was generated to exclusively catalyze selective monohalogenation. We propose a novel dual‐activation mechanism and demonstrate that the larger binding pocket of FasV makes it a valuable biocatalyst for other substrates with diverse structures. Therefore, this study provides new insight into multi‐site polyhalogenases and highlights the potential for engineering FasV‐like FDHs for biocatalytic applications.
Enhancing Mechanical Durability and Long‐Term Stability in Organic Solar Cells via Flexible Linker‐Sequential Block Copolymerized Donors
Authors: Lin Congqi , Peng Ruixiang , Song Wei , Gao Jiangwei , Feng Tingting , Bai Yongqi , Liu Quan , Yang Mengjin , Zhang Jianfeng , Ge Ziyi 
Published: November 2024

AbstractMulti‐component copolymerized donors (MCDs) hold great promise for improving both the efficiency and mechanical robustness of flexible organic solar cells (f‐OSCs) owing to their facile molecular tunability and advantageous one‐pot copolymerization. However, despite the excellent crystallinity imparted by their highly conjugated polymer backbone, MCDs often struggle to retain photovoltaic performance under large external deformations, limiting their applicability in wearable devices. Herein, we developed a novel series of flexible linker‐sequential block MCDs (Fs‐MCDs), specifically PM6‐Cl0.8‐b‐D18‐Cl0.2‐BTB, PM6‐Cl0.8‐b‐D18‐Cl0.2‐BTH, and PM6‐Cl0.8‐b‐D18‐Cl0.2‐BTD, by precisely incorporating flexible functional groups into the conjugated polymer skeleton. This design strategy introduced highly effective tensile active sites, resulting in remarkable mechanical durability, with PM6‐Cl0.8‐b‐D18‐Cl0.2‐BTD achieving crack‐onset strain (COS) values of 49.88 % in pristine films and 31.29 % in blends. The nearly 50 % COS in pristine films represents one of the highest values reported for Fs‐MCD‐based OSCs, marking a significant milestone in advancing f‐OSC. Additionally, PM6‐Cl0.8‐b‐D18‐Cl0.2‐BTD demonstrated excellent photovoltaic performance, with efficiencies of 18.09 % in rigid binary and 19.05 % in ternary, as well as 16.63 % in flexible OSCs. It also showed impressive device stability in invert OSC (T80=9,078 h). This unique molecular design strategy provides a promising avenue for synergistically improving the photovoltaic performance, mechanical properties, and device stability of f‐OSCs.
Lignin‐Based Type I Macromolecular Photoinitiator for Fabricating UV‐Blocking Films
Authors: Qi Yujie , Zhai Haoqi , Huang Xing , Shi Mengquan , Zhang Yuxi , Zhao Yuxia 
Published: November 2024

ABSTRACTAs the largest renewable source of aromatic feedstock in nature, lignin has good thermal stability, strong ultraviolet (UV) absorption, and mechanical reinforcing property. In this study, a lignin‐based Type I macromolecular photoinitiator (macro PI) named DAL‐11ene‐TPO is designed and synthesized through covalently grafting 10‐undecenoyl chloride (11ene) and 2,4,6‐trimethylbenzoyl‐ethoxy‐phenylphosphine oxide (TPO‐L, a commercial small molecular PI) into dealkaline lignin (DAL) skeleton. A series of characterizations were performed to prove that DAL‐11ene‐TPO was synthesized successfully, including 1H NMR, FTIR, UV–vis, 31P NMR, GPC (gel permeation chromatography). The formed active free radicals were monitored by electron spin resonance (ESR). DAL‐11ene‐TPO can high‐efficiently initiate the monomers polymerization upon the irradiation of 405 nm LED. The resulting polymer films showed strong UV‐blocking performance and good visible light transmittance. Moreover, the elongation at break of the polymer film containing 0.5% DAL‐11ene‐TPO is improved by 50% compared with that of TPO‐L control group. Furthermore, DAL‐11ene‐TPO has polymerizable groups, which can be bonded into the network of the polymers, resulting in a high biosafety of the end products. The results indicate that DAL‐11ene‐TPO can be used as a high‐efficient bio‐based macro PI for preparing high performance UV‐blocking films.
Substitution of Glutamic Acid at Position 71 of DRβ1*04:01 and Collagen‐Specific Tolerance Without Alloreactivity
Authors: Jha Vibha , Freed Brian M. , Sunderhaus Elizabeth R. , Lee Jessica E. , Prage Edward B. , Miglani Manjula , Rosloniec Edward F. , Matsuda Jennifer L. , Coulombe Marilyne G. , McKee Amy S. , Roark Christina L. 
Published: November 2024

ObjectiveThe DRB1 locus is strongly associated with both susceptibility and resistance to rheumatoid arthritis (RA). DRB1 alleles encoding the VKA or VRA epitope in positions 11, 71, and 74 confer the highest risk of developing RA, whereas the allele encoding VEA is protective. We therefore investigated the feasibility of creating antigen‐specific tolerance without inducing alloreactivity by replacing lysine with glutamic acid at position 71 in DRβ1*04:01.MethodsIndividual DRB1 alleles and the DRB1*04:01K71E allele were cloned into T2 cell lines to measure binding of biotinylated peptides. Transgenic animals expressing DRB1*04:01, DRB1*01:01, or DRB1*04:01K71E were injected with collagen to measure T cell proliferation. Skin and bone marrow transplants between DRB1*04:01K71E and DRB1*04:01 mice were performed to determine if the single amino acid change at position 71 would be recognized as foreign. DRB1*04:01 mice transplanted with DRB1*04:01K71E bone marrow were injected with collagen to test if resistance to collagen sensitization could be transferred.ResultsReplacing lysine (K) at position 71 in DRβ1*04:01 with glutamic acid (E) blocked collagen peptide binding and rendered the DRB1*04:01K71E mice resistant to collagen sensitization. Skin and bone marrow transplants from DRB1*04:01K71E mice were not rejected by DRB1*04:01 mice, suggesting the single E71 difference was not recognized as allogeneic. Bone marrow from DRB1*04:01K71E mice adoptively transferred antigen‐specific tolerance to collagen to DRB1*04:01 mice.ConclusionThese studies demonstrate that editing a single amino acid in DRβ1*04:01 blocks collagen peptide binding without inducing alloreactivity and could therefore represent a gene therapy approach to induce antigen‐specific passive tolerance.
A Facile and Efficient Synthesis of BODIPY‐Based Fluorescent Probes for Selective Detection of Hydrazine
Authors: Saraf Prakriti , Shrivastava Pragati , Sarkar Madhushree , Kumar Dalip 
Published: November 2024

AbstractA facile and ratiometric BODIPY‐based fluorescent probe 4 was developed for the selective detection of hydrazine in solution phase. The BODIPY‐based fluorophores 3 and 4 were easily prepared in high yields from the L‐proline catalyzed reaction between α/β‐formyl BODIPY 1 a/1 b and 3‐cyanoacetylindole 2. Use of easily accessible substrates, benign solvent, catalytic amount of L‐proline and high product yields are the advantageous features of the developed protocol. Prepared BODIPYs 3 (536 nm) and 4 (567 nm) showed bathochromic shifts (36–67 nm) in UV‐Visible absorption maxima when compared to parent BODIPY (500 nm) in dichloromethane (DCM). The stable and economical BODIPY‐based probe 4 exhibited rapid response and remarkable selectivity towards hydrazine when compared to other commonly occurring analytes. At low concentration, the BODIPY probe 4 (10 μΜ) is non‐fluorescent, however, a significant enhancement in fluorescent (turn‐on) was observed with the increasing concentration of hydrazine (0–100 μΜ). This change in fluorescent behaviour may be ascribed to intramolecular charge transfer (ICT) effect as supported by density functional theory (DFT) calculations. With a 4.3 μM detection limit, the BODIPY probe 4 was also found to be useful in detecting hydrazine in real environmental samples.
Photoresponsive Luminescent Silica Nanoparticles as Additive for 3D Printing and Electrospinning
Authors: Lorberg Rick Y. , Nair Sailaja Sidharth Thulaseedharan , Terlau Fabian , Victoria Cappellari Maria , Schmiedtchen Marco , Galstyan Anzhela , Strassert Cristian A. , Giese Michael , Voskuhl Jens 
Published: November 2024

AbstractIn this study, we present the synthesis and a versatile way to incorporate photoresponsive organic luminophores into polymeric materials using mesoporous silica nanoparticles (MSNs). The encapsulated thioethers within the MSNs were employed in polyvinyl alcohol (PVA) films, resin‐based stereolithography, and electrospinning. Due to light‐induced cyclisation to dibenzothiophenes (DBTs), mmOC12 loaded materials were used to inscribe images using UV light. The DBTs formed from mmOC12 (mmDBTA/B) exhibit a long phosphorescence afterglow, which was investigated by steady‐state and time‐resolved photoluminescence spectroscopy. In addition, scanning electron microscopy (SEM) imaging, including energy dispersive X‐ray spectroscopy (EDX), revealed the well‐dispersed and intact MSNs in the polymeric materials. This approach shows a general way to incorporate non‐polar organic luminophores into polymeric materials while retaining their unique emission properties.
Regulation of classical zinc fingers for neuronal signaling in the central nervous system
Authors: Hwang Yunha , Park Soyeon , Kim Hyunyong , Park Yerim , Kang Hyun Goo , Lee Dong‐Heon , Lee Seung Jae 
Published: November 2024

AbstractZinc finger (ZF) proteins are well‐known for their regulatory functions in the central dogma, and their structural domains serve as promising scaffolds for the study of neurodegenerative diseases. These proteins often contain multiple ZF domains, enabling interactions with target molecules that regulate transcription and translation. The Cys2His2 (C2H2) type ZF domains, found in the brain, are associated with long‐ and short‐term memory, neuronal differentiation and development, and other physiological processes. The classical C‐X2‐C‐X12‐H‐X3‐H type ZF domains have been detected in studies of Parkinson's disease (PD) and are closely linked to biological pathways involved in a wide range of neurodegenerative diseases. In this review, we introduce three ZF proteins expressed in the brain: Parkin‐interacting substrate (PARIS), zinc finger and BTB domain‐containing 20 (ZBTB20), and zinc finger protein 18 (ZNF18). We explore the structural and functional roles of these ZF proteins in the brain. Each of these proteins contains more than four ZF domains, as well as functional domains such as KRAB, BTB, and SCAN, which perform modular roles independently of the ZF domains. Biophysical studies of PARIS have demonstrated that its classical three‐ZF domain, PARIS(ZF2–4), forms hydrogen bonds with insulin response sequences (IRSs) with high specificity (Kd = 38.9 ± 2.4 nM). Metal coordination studies showed that PARIS binds Co2+ with high affinity (Kd = 49.1 ± 7.7 nM), more strongly than other ZF domains, and it also coordinates with other xenobiotic metal ions such as Fe2+ and Ni2+. Although Zn2+–PARIS(ZF2–4) binds specifically to IRSs, Fe2+–, Fe3+– or Co2+–PARIS(ZF2–4) cannot, due to distortions in the ZF domain structure that disrupt hydrogen bonding. These brain‐specific ZF domains exhibit common patterns, with similar numbers of ZF domains and sequence homology at the C‐terminus, whereas both the ZF domains and N‐terminal protein–protein interaction domains contribute to their functional versatility. Elucidating the structure and function of these classical ZF proteins offers promising avenues for the treatment of diverse brain disorders, including Alzheimer's disease, PD, and autism spectrum disorder.