bluuebunny/crossref_metadata_2025_split huggingface dataset:
Dynamic Covalent Adaptable Polyimide Hybrid Dielectric Films with Superior Recyclability
Authors: Wan Baoquan , Xiao Mengyu , Dong Xiaodi , Yang Xing , Zheng Ming‐Sheng , Dang Zhi‐Min , Chen George , Zha Jun‐Wei 
Published: June 2023

AbstractPolyimides (PIs) used in advanced electrical and electronic devices can be electrically/mechanically damaged, resulting in a significant waste of resources. Closed‐loop chemical recycling may prolong the service life of synthetic polymers. However, the design of dynamic covalent bonds for preparing chemically recyclable crosslinked PIs remains a challenging task. Herein, new crosslinked PI films containing a PI oligomer, chain extender, and crosslinker are reported. They exhibit superior recyclability and excellent self‐healable ability owing to the synergistic effect of the chain extender and crosslinker. The produced films can be completely depolymerized in an acidic solution at ambient temperature, leading to efficient monomer recovery. The recovered monomers may be used to remanufacture crosslinked PIs without deteriorating their original performance. In particular, the designed films can serve as corona‐resistant films with a recovery rate of approximately 100%. Furthermore, carbon fiber reinforced composites (CFRCs) with PI matrices are suitable for harsh environments and can be recycled multiple times at a non‐destructive recycling rate up to 100%. The preparation of high‐strength dynamic covalent adaptable PI hybrid films from simple PI oligomers, chain extenders, and crosslinkers may provide a solid basis for sustainable development in the electrical and electronic fields.
Trivalent Phosphine‐Catalyzed Reactions Using Fluorinated Building Blocks
Authors: Li Yi‐Chao , Wang Yu‐Hao , Jyoti Kalita Subarna , Huang Yi‐Yong 
Published: June 2023

AbstractThe development of novel synthetic methodologies to incorporate fluorine/s or fluoroalkyl group/s into the frameworks of organic molecules has become a highly prioritized research area because such modifications can tune their physiochemical and biological properties. In recent years, nucleophilic phosphine catalysis has been extensively explored to achieve this goal, and significant progress has been made. This review summarizes the methodological advancements of cycloaddition, addition and coupling reactions employing fluorinated building blocks as electrophilic and/or nucleophilic reaction partners under phosphine catalysis to construct structurally and synthetically valuable organofluorine compounds, with special emphasis on the synthetic strategies, proposed reaction mechanisms and synthetic utilities.
Development and Assessment of Computational Models Detailing the Influence of Extra‐Framework Cations on the Local Structure, Stability and Structure‐Property Relationships in Geopolymers
Authors: Misra Swayam Prabha , Deshpande Parag A. 
Published: June 2023

AbstractThis study presents density functional theory based computational analysis of geopolymeric materials of varied Si:Al ratios and extra‐framework cations. Due to the absence of crystallinity and long‐range order in geopolymers, no standard molecular models are present for quantum chemical analysis of these materials. Therefore, computationally feasible molecular models conforming to experimental reports and constraints are developed that accounted for all combinatorially possible local structures in the material. The computational analysis conclusively proved the effect of Si:Al ratio and the identity of the extra‐framework cation on the stability of the material with Si:Al = 2:1 decorated with Ca2 + ions exhibiting the highest stability. No significant effect of local structure is observed on the stability of the systems. Insights into the stability and adsorption property are developed on the basis of partial charge distribution thereby providing the details on the effects of constituent elements on the structure‐property relationships in geopolymers.
Monomicelle‐Directed Engineering of Strained Carbon Nanoribbons as Oxygen Reduction Catalyst
Authors: Xue Dongping , Guo Yingying , Lu Bang‐An , Xia Huicong , Yan Wenfu , Xue Dongfeng , Mu Shichun , Zhang Jia‐Nan 
Published: June 2023

AbstractTo date, precisely tailoring local active sites of well‐defined earth‐abundant metal‐free carbon‐based electrocatalysts for attractive electrocatalytic oxygen reduction reaction (ORR), remains challenging. Herein, the authors successfully introduce a strain effect on active C–C bonds adjacent to edged graphitic nitrogen (N), which raises appropriate spin‐polarization and charge density of carbon active sites and kinetically favor the facilitation of O2 adsorption and the activation of O‐containing intermediates. Thus, the constructed metal‐free carbon nanoribbons (CNRs‐C) with high‐curved edges exhibit outstanding ORR activity with half‐wave potentials of 0.78 and 0.9 V in 0.5 m H2SO4 and 0.1 m KOH, respectively, overwhelming the planar one (0.52 and 0.81 V) and the N‐doped carbon sheet (0.41 and 0.71 V). Especially in acidic media, the kinetic current density (Jk) is 18 times higher than that of the planar one and the N‐doped carbon sheet. Notably, these findings show the spin polarization of the asymmetric structure by introducing a strain effect on the C–C bonds for boosting ORR.
Controllable Etching of Ti3SiC2 to Produce Fluorine‐Enriched, Hydrophobic 2D Titanium Carbide for Ultrastable Zinc Ion Batteries
Authors: Guo Yu , Gao Yuxuan , Chen Hao , Zhao Qi , Zhu Qi , Cao Zhenjiang , Li Bin , Shang Jiaxiang , Du Zhiguo , Yang Shubin 
Published: June 2023

AbstractMXenes are mainly produced via selectively etching MAX phases in aqueous F‐containing solutions, commonly showing a highly hydrophilic character due to their plentiful ‐O and ‐OH terminations. However, the hydrophilic nature of MXenes may deteriorate their durability and stability as employed in humid and aqueous environments. Here, this work demonstrates a new etching approach to produce fluorine‐enriched MXene Ti3C2Fx via selective etching of Si from Ti3SiC2 in sulfur hexafluoride (SF6) gas. During the etching process, SF6 enables the selective removal of Si species with the formation of volatile SiF4 and efficiently reacts with the exposed surface of Ti3C2 slabs, affording Ti3C2Fx MXene with a fraction of ‐F termination up to 87 at.% and good hydrophobicity. Such hydrophobic Ti3C2Fx MXene is beneficial to suppress water‐induced side reactions and decrease the Zn nucleation energy barrier, delivering a long cyclic lifespan of 1200 h and superior rate performance up to 6.4 mA cm−2 in Ti3C2Fx/Zn symmetric cells. Coupled with nickel hexacyanoferrate (NiHCF) as a cathode, the zinc full cell with Ti3C2Fx/Zn anode exhibits good rate capabilities (58 mAh g−1, 3.2 A g−1) and long cycling stability up to 1000 cycles at 3.2 A g−1.
In Situ Transmission Electron Microscopy Observation of Melted Germanium Encapsulated in Multilayer Graphene
Authors: Suzuki Seiya , Nemoto Yoshihiro , Shiiki Natsumi , Nakayama Yoshiko , Takeguchi Masaki 
Published: June 2023

AbstractGermanene is a two‐dimensional germanium (Ge) analogous of graphene, and its unique topological properties are expected to make it a material for next‐generation electronics. However, no germanene electronic devices have yet been reported. One of the reasons for this is that germanene is easily oxidized in air due to its lack of chemical stability. Therefore, growing germanene at solid interfaces where it is not oxidized is one of the key steps for realizing electronic devices based on germanene. In this study, the behavior of Ge at the solid interface at high temperatures is observed by transmission electron microscopy (TEM). To achieve such in situ heating TEM observation, this work fabricates a graphene/Ge/graphene encapsulated structure. In situ heating TEM experiments reveal that Ge like droplets move and coalesce with other Ge droplets, indicating that Ge remains as a liquid phase between graphene layers at temperatures higher than the Ge melting point. It is also observed that Ge droplets incorporate the surrounding amorphous Ge as Ge nuclei, thereby increasing its size (domain growth). These results indicate that Ge crystals can be grown at the interface of van der Waals materials, which will be important for future germanene growth at solid interfaces.
On the Conformation of Dimeric Acceptors and Their Polymer Solar Cells with Efficiency over 18 %
Authors: Wu Jingnan , Ling Zhaoheng , Franco Leandro R. , Jeong Sang Young , Genene Zewdneh , Mena Josué , Chen Si , Chen Cailing , Araujo C. Moyses , Marchiori Cleber F. N. , Kimpel Joost , Chang Xiaoming , Isikgor Furkan H. , Chen Qiaonan , Faber Hendrik , Han Yu , Laquai Frédéric , Zhang Maojie , Woo Han Young , Yu Donghong , Anthopoulos Thomas D. , Wang Ergang 
Published: June 2023

AbstractThe determination of molecular conformations of oligomeric acceptors (OAs) and their impact on molecular packing are crucial for understanding the photovoltaic performance of their resulting polymer solar cells (PSCs) but have not been well studied yet. Herein, we synthesized two dimeric acceptor materials, DIBP3F‐Se and DIBP3F‐S, which bridged two segments of Y6‐derivatives by selenophene and thiophene, respectively. Theoretical simulation and experimental 1D and 2D NMR spectroscopic studies prove that both dimers exhibit O‐shaped conformations other than S‐ or U‐shaped counter‐ones. Notably, this O‐shaped conformation is likely governed by a distinctive “conformational lock” mechanism, arising from the intensified intramolecular π–π interactions among their two terminal groups within the dimers. PSCs based on DIBP3F‐Se deliver a maximum efficiency of 18.09 %, outperforming DIBP3F‐S‐based cells (16.11 %) and ranking among the highest efficiencies for OA‐based PSCs. This work demonstrates a facile method to obtain OA conformations and highlights the potential of dimeric acceptors for high‐performance PSCs.
Adamantoid Scaffolds for Multiple Cargo Loading and Cellular Delivery as β‐Cyclodextrin Inclusion Complexes
Authors: Ravi Arthi , Pathigoolla Atchutarao , Balan Haripriya , Gupta Ria , Raj Gowtham , Varghese Reji , Sureshan Kana M. 
Published: June 2023

AbstractThere is huge demand for developing guests that bind β‐CD and can conjugate multiple cargos for cellular delivery. We synthesized trioxaadamantane derivatives, which can conjugate up to three cargos per guest. 1H NMR titration and isothermal titration calorimetry revealed these guests form 1 : 1 inclusion complexes with β‐CD with association constants in the order of 103 M−1. Co‐crystallization of β‐CD with guests yielded crystals of their 1 : 1 inclusion complexes as determined by single‐crystal X‐ray diffraction. In all cases, trioxaadamantane core is buried within the hydrophobic cavity of β‐CD and three hydroxyl groups are exposed outside. We established biocompatibility using representative candidate G4 and its inclusion complex with β‐CD (β‐CD⊂G4), by MTT assay using HeLa cells. We incubated HeLa cells with rhodamine‐conjugated G4 and established cellular cargo delivery using confocal laser scanning microscopy (CLSM) and fluorescence‐activated cell sorting (FACS) analysis. For functional assay, we incubated HeLa cells with β‐CD‐inclusion complexes of G4‐derived prodrugs G6 and G7, containing one and three units of the antitumor drug (S)‐(+)‐camptothecin, respectively. Cells incubated with β‐CD⊂G7 displayed the highest internalization and uniform distribution of camptothecin. β‐CD⊂G7 showed higher cytotoxicity than G7, camptothecin, G6 and β‐CD⊂G6, affirming the efficiency of adamantoid derivatives in high‐density loading and cargo delivery.
Prolinyl Nucleotides Drive Enzyme‐Free Genetic Copying of RNA
Authors: Welsch Franziska , Kervio Eric , Tremmel Peter , Richert Clemens 
Published: June 2023

AbstractProline is one of the proteinogenic amino acids. It is found in all kingdoms of life. It also has remarkable activity as an organocatalyst and is of structural importance in many folded polypeptides. Here, we show that prolinyl nucleotides with a phosphoramidate linkage are active building blocks in enzyme‐ and ribozyme‐free copying of RNA in the presence of monosubstituted imidazoles as organocatalysts. Both dinucleotides and mononucleotides are incorporated at the terminus of RNA primers in aqueous buffer, as instructed by the template sequence, in up to eight consecutive extension steps. Our results show that condensation products of amino acids and ribonucleotides can act like nucleoside triphosphates in media devoid of enzymes or ribozymes. Prolinyl nucleotides are metastable building blocks, readily activated by catalysts, helping to explain why the combination of α‐amino acids and nucleic acids was selected in molecular evolution.
Transient Transcription Machineries Modulate Dynamic Functions of G‐Quadruplexes: Temporal Regulation of Biocatalytic Circuits, Gene Replication and Transcription
Authors: Dong Jiantong , Willner Itamar 
Published: June 2023

AbstractNative G‐quadruplex‐regulated temporal biocatalytic circuits, gene polymerization, and transcription processes are emulated by biomimetic, synthetically engineered transcription machineries coupled to reconfigurable G‐quadruplex nanostructures. These are addressed by the following example: (i) A reaction module demonstrates the fuel‐triggered transcription machinery‐guided transient synthesis of G‐quadruplex nanostructures. (ii) A dynamically triggered and modulated transcription machinery that guides the temporal separation and reassembly of the anti‐thrombin G‐quadruplex aptamer/thrombin complex is introduced, and the transient thrombin‐catalyzed coagulation of fibrinogen is demonstrated. (iii) A dynamically fueled transient transcription machinery for the temporal activation of G‐quadruplex‐topologically blocked gene polymerization circuits is introduced. (iv) Transcription circuits revealing G‐quadruplex‐promoted or G‐quadruplex‐inhibited cascaded transcription machineries are presented. Beyond advancing the rapidly developing field of dynamically modulated G‐quadruplex DNA nanostructures, the systems introduce potential therapeutic applications.
A policy and research agenda for Asia's poultry industry
Authors: Mahanty Sango , Doron Assa , Hamilton Rebecca 
Published: June 2023

AbstractMeat consumption and production in Asia have boomed over the last decade to meet growing regional and global demand. Asia now supplies around 40% of the global broiler or meat chicken industry. Dominant policy frameworks such as ‘One Health’ aim to manage the health risks associated with factory livestock farming, which has rightly become a major concern because of regular disease outbreaks. Yet this approach provides a limited basis for addressing broader risks and challenges associated with what we term the Asian ‘broiler complex’. This includes the intertwined networks of feed production, factory farming and meat distribution nodes through which health and environmental risks can accumulate and be amplified. By applying this broader lens, we highlight the need to better understand the industry's pressing environmental, animal welfare, social and health challenges to inform more integrated policy approaches.
Development of On‐DNA Cyclic Imide Synthesis for DNA Encoded Library Construction
Authors: Xue Lijun , Zhou Sufang , Wu Jing , Duchemin Nicolas , Chen Bingxin , Zhang Jie , Zhang Huanqing , Yang Kexin , Hu Yun Jin 
Published: June 2023

AbstractHere, we describe a novel method for the on‐DNA synthesis of cyclic imides, an important class of molecules that includes several well‐known medications. Significantly, the new method enabled on‐DNA synthesis under mild conditions with high conversions and a broad functional group tolerance, utilizing ubiquitous bifunctional amines and bis‐carboxylic acid, or alkyl halides, and therefore served as the linchpin for DNA encoded library (DEL) synthesis. The mechanism study of off‐DNA and on‐DNA chemical transformations revealed unique insights in contrast to conventional chemical transformation.
Platinum and Palladium Organometallic Compounds: Disrupting the Ergosterol Pathway in Trypanosoma cruzi
Authors: Mosquillo Florencia , Scalese Gonzalo , Moreira Rodrigo , Denis Pablo A. , Machado Ignacio , Paulino Margot , Gambino Dinorah , Pérez‐Díaz Leticia 
Published: June 2023

AbstractCurrent treatment for Chagas’ disease is based on two drugs, Nifurtimox and Benznidazol, which have limitations that reduce the effectiveness and continuity of treatment. Thus, there is an urgent need to develop new, safe and effective drugs. In previous work, two new metal‐based compounds with trypanocidal activity, Pd‐dppf‐mpo and Pt‐dppf‐mpo, were fully characterized. To unravel the mechanism of action of these two analogous metal‐based drugs, high‐throughput omics studies were performed. A multimodal mechanism of action was postulated with several candidates as molecular targets. In this work, we validated the ergosterol biosynthesis pathway as a target for these compounds through the determination of sterol levels by HPLC in treated parasites. To understand the molecular level at which these compounds participate, two enzymes that met eligibility criteria at different levels were selected for further studies: phosphomevalonate kinase (PMK) and lanosterol 14‐α demethylase (CYP51). Molecular docking processes were carried out to search for potential sites of interaction for both enzymes. To validate these candidates, a gain‐of‐function strategy was used through the generation of overexpressing PMK and CYP51 parasites. Results here presented confirm that the mechanism of action of Pd‐dppf‐mpo and Pt‐dppf‐mpo compounds involves the inhibition of both enzymes.
Photoactivation of Solid‐State Fluorescence through Controllable Intermolecular [2+2] Photodimerization
Authors: Ping Xinni , Zhan Jiale , Zhu Yuqing , Wu Yuzhen , Hu Caiyi , Pan Junjun , Yao Chuangye , Zuo Jiaqi , Feng Hui , Qian Zhaosheng 
Published: June 2023

AbstractIntermolecular [2+2] photodimerization provides a distinctive approach to construct photoresponsive fluorescent materials in a manner of switching on solid‐state fluorescence. Herein, we report efficient photoactivation of bright solid‐state fluorescence based on controllable intermolecular [2+2] photodimerization reaction of benzo[b]thiophene 1,1‐dioxide (BTO) derivatives, which provides a simple and effective way to construct smart photoresponsive solid‐state fluorescent materials. Rational choice of substituents in BTO molecular skeleton enables them to efficiently undergo photodimerization through regulating molecular stacking in crystal, and also leads to photoactivation of solid‐state fluorescence due to the generation of brightly fluorescent photodimers. This intermolecular photodimerization reaction also offers an effective method to synthesize photostable AIEgens with purely through‐space conjugation.
Performance evaluation of different types of surfactants to inhibit clay swelling during chemical enhanced oil recovery
Authors: Khezerloo‐ye Aghdam Saeed , Kazemi Alireza , Ahmadi Mohammad 
Published: June 2023

AbstractIn most cases, sandstone reservoirs contain clay particles. When a fluid with low salt content is injected into the reservoir, clay particles swell, and the rock's permeability decreases. Since surfactant flooding with water that has lower salinity than formation water is used to improve oil recovery, this study examines the swelling inhibitive strength of various surfactants. The study investigates the effect of surfactants on clay swelling inhibition through linear swelling and sedimentation experiments which showed that cetyl trimethyl ammonium bromide (CTAB) inhibits clay swelling. The optimum CTAB concentration was found to be 1 wt.%. However, sodium dodecyl sulphate (SDS) and Triton X‐100 (TX‐100) did not inhibit clay swelling. Sandpack experiments confirmed that CTAB prevented clay swelling and sandpack permeability reduction, while SDS and TX‐100 did not. The injection pressure results for the different surfactants were as follows: CTAB—39 psi, SDS—203 psi, TX‐100—223 psi, deionized water (DW)—324 psi, and KCl—78 psi. The mechanism of surfactant performance in affecting clay swelling was investigated based on thermal gravimetric analysis (TGA), zeta potential, and scanning electron microscope (SEM) images. The results showed that CTAB compensates for the surface charge of clays through a cation exchange mechanism. The amount of absorbed water for clays modified with CTAB was lower than that for other surfactants. The SEM images confirmed that the CTAB‐modified clays were larger and did not disintegrate during dispersion; however, in other cases, the particle size was smaller.
Ethyl ester production with immobilized lipase in tin modified SBA‐15: Effect of the support characteristic and reaction conditions
Authors: Parmegiani Marcucci Sílvio Miguel , Zunta Raia Rodrigo , Zanin Gisella Maria , Arroyo Pedro Augusto 
Published: June 2023

AbstractThis study investigated the use of immobilized lipase in SBA‐15 and pore‐expanded SBA‐15 surface modified with tin, denoted as SnS23B (mean pore size of 21.6 nm) and SnS8B (with mean pore size of 9.6 nm), respectively, to produce ethyl esters. The effects of various reaction parameters, including biocatalyst type, oil (refined and degummed soybean oil), water addition, oil‐to‐ethanol molar ratio, immobilized lipase concentration, agitation speed, reaction temperature, and glycerol addition, were examined. The optimal conditions were found to be the use of SnS23B as the biocatalyst, degummed soybean oil as the substrate, 1% (w/w oil) water, 1:3 oil‐to‐ethanol molar ratio, 5% (w/w oil) immobilized lipase, 800 rpm agitation speed, and 25°C reaction temperature. The presence of glycerol negatively impacted the reaction. Under the optimal conditions, the mass percent of ethyl ester obtained was 98.2% ± 0.16. The immobilized lipase showed stability, as no lipase activity was detected upon removing the biocatalyst from the reaction. However, the biocatalyst lost 50% of its activity after 10 successive reactions, likely due to thermal deactivation and lipase inhibition caused be the adsorption of glycerol and other chemical species. Attenuated total reflectance analysis supported this hypothesis.
Effects of sacubitril‐valsartan in the treatment of chronic heart failure patients with end‐stage renal disease undergoing dialysis
Authors: Liu Xiaoyan , Huang Lidong , Tse Gary , Liu Tong , Che Jingjin 
Published: June 2023

AbstractBackgroundThe data on the effects of the angiotensin receptor–neprilysin inhibitor (ARNI) sacubitril‐valsartan (LCZ696) in chronic heart failure (CHF) patients with end‐stage renal disease (ESRD) requiring dialysis are lacking. This study assessed the efficacy and safety of LCZ696 in CHF patients with ESRD on dialysis.HypothesisLCZ696 treatment can reduce rehospitalization rate for HF, delay the occurrence of rehospitalization for HF, and prolong the survival time.MethodsWe retrospectively analyzed the clinical data of CHF patients with ESRD on dialysis who were admitted to the Second Hospital of Tianjin Medical University from August 2019 to October 2021.ResultsSixty‐five patients had primary outcome during the follow‐up. The incidence of rehospitalization for HF in the control group was significantly higher than that in the LCZ696 group (73.47% vs. 43.28%, p = .001). There was no significant difference in mortality between the two groups (8.96% vs. 10.20%, p = 1.000). Our study included a time‐to‐event analysis through 1 year for the primary outcome—Kaplan–Meier curve showed that the LCZ696 group had significantly longer free‐event survival time than the control group over 1‐year follow‐up (median survival time 139.0 days vs. 116.0 days, p = .037).ConclusionsOur study found that LCZ696 treatment was associated with a reduction in HF rehospitalization without significant effects on serum creatinine and serum potassium levels. LCZ696 is effective and safe in CHF patients with ESRD on dialysis.