bluuebunny/crossref_metadata_2025_split huggingface dataset:
Contact‐Electro‐Catalysis for Direct Oxidation of Methane under Ambient Conditions
Authors: Li Weixin , Sun Jikai , Wang Mingda , Xu Jiajia , Wang Yanjie , Yang Li , Yan Ran , He Haoxian , Wang Shuai , Deng Wei‐Qiao , Tian Zhong‐Qun , Fan Feng Ru 
Published: March 2024

AbstractThe conversion of methane under ambient conditions has attracted significant attention. Although advancements have been made using active oxygen species from photo‐ and electro‐ chemical processes, challenges such as complex catalyst design, costly oxidants, and unwanted byproducts remain. This study exploits the concept of contact‐electro‐catalysis, initiating chemical reactions through charge exchange at a solid–liquid interface, to report a novel process for directly converting methane under ambient conditions. Utilizing the electrification of commercially available Fluorinated Ethylene Propylene (FEP) with water under ultrasound, we demonstrate how this interaction promote the activation of methane and oxygen molecules. Our results show that the yield of HCHO and CH3OH can reach 467.5 and 151.2 μmol ⋅ gcat−1, respectively. We utilized electron paramagnetic resonance (EPR) to confirm the evolution of hydroxyl radicals (⋅OH) and superoxide radicals (⋅OOH). Isotope mass spectrometry (MS) was employed to analyze the elemental origin of CH3OH, which can be further oxidized to HCHO. Additionally, we conducted density functional theory (DFT) simulations to assess the reaction energies of FEP with H2O, O2, and CH4under these conditions. The implications of this methodology, with its potential applicability to a wider array of gas‐phase catalytic reactions, underscore a significant advance in catalysis.
Manganese(I)‐Catalyzed Enantioselective C(sp2)−C(sp3) Bond‐Forming for the Synthesis of Skipped Dienes with Synergistic Aminocatalysis
Authors: Zhao Chuan‐Gang , Cai Junzhe , Du Chaoyu , Gao Qi , Han Jie , Xie Jin 
Published: March 2024

AbstractMn(I)‐catalyzed enantioselective C−C bond‐forming reactions represent a great challenge in homogeneous catalysis primarily due to a limited understanding of its mechanistic principles. Herein, we have developed an interesting catalytic strategy that leverages a synergistic combination of a dimeric manganese(I) catalyst and a chiral aminocatalyst to address this issue. A range of conjugated dienals and trienals can exclusively proceed 1,4‐hydroalkenylation by using readily available aromatic and aliphatic alkenyl boronic acids as coupling partners, producing a rich library of skipped diene aldehydes in synthetically useful yields and high levels of enantioselectivities. Notably, downstream transformations of these products can not only afford a concise approach to construct enantioenriched skipped trienes but also realize enantioselective total synthesis of analogues to (−)‐Blepharocalyxin D in four steps. DFT calculations suggest the 1,4‐hydroalkenylation is kinetically more favorable than 1,6‐hydroalkenylation.
Elastic Relaxor Ferroelectric by Thiol‐ene Click Reaction
Authors: Li Bowen , Wang Linping , Gao Liang , Xu Tianhua , Zhang Dongyang , Li Fangzhou , Lyu Jike , Zhu Ren , Gao Xin , Zhang Heng , Hu Ben‐Lin , Li Run‐Wei 
Published: March 2024

AbstractAs ferroelectrics hold significance and application prospects in wearable devices, the elastification of ferroelectrics becomes more and more important. Nevertheless, achieving elastic ferroelectrics requires stringent synthesis conditions, while the elastification of relaxor ferroelectric materials remains unexplored, presenting an untapped potential for utilization in energy storage and actuation for wearable electronics. The thiol‐ene click reaction offers a mild and rapid reaction platform to prepare functional polymers. Therefore, we employed this approach to obtain an elastic relaxor ferroelectric by crosslinking an intramolecular carbon‐carbon double bonds (CF=CH) polymer matrix with multiple thiol groups via a thiol‐ene click reaction. The resulting elastic relaxor ferroelectric demonstrates pronounced relaxor‐type ferroelectric behaviour. This material exhibits low modulus, excellent resilience, and fatigue resistance, maintaining a stable ferroelectric response even under strains up to 70 %. This study introduces a straightforward and efficient approach for the construction of elastic relaxor ferroelectrics, thereby expanding the application possibilities in wearable electronics.
N‐Heteroaromatic Fluoroalkylation through Ligand Coupling Reaction of Sulfones
Authors: Liang Huamin , Wang Qian , Zhou Xin , Zhang Rongyi , Zhou Min , Wei Jun , Ni Chuanfa , Hu Jinbo 
Published: March 2024

AbstractLigand coupling on hypervalent main group elements has emerged as a pivotal methodology for the synthesis of functionalized N‐heteroaromatic compounds in recent years due to the avoidance of transition metals and the mildness of the reaction conditions. In this direction, the reaction of N‐heteroaryl sulfur(IV) and N‐heteroaryl phosphorus(V) compounds has been well studied. However, the ligand coupling of sulfur(VI) is still underdeveloped and the reaction of alkyl N‐heteroarylsulfones is still elusive, which does not match the high status of sulfones as the chemical chameleons in organic synthesis. Here we present a ligand coupling‐enabled formal SO2 extrusion of fluoroalkyl 2‐azaheteroarylsulfones under the promotion of Grignard reagents, which not only enriches the chemistry of sulfones, but also provides a novel and practical synthetic tool towards N‐heteroaromatic fluoroalkylation.
Water‐Soluble Fluorescent Polymer Dyes with Tunable Emission Spectra for Flow Cytometry Applications
Authors: Berndt Daniel , Glaap Dorina , Jennings Travis , Dose Christian , Werz Daniel B. , Reckert Dirk N. H. 
Published: March 2024

AbstractThe application of spectrally unique, bright, and water‐soluble fluorescent dyes is indispensable for the analysis of biological systems. Multiparameter flow cytometry is a powerful tool for characterization of mixed cell populations. To discriminate the different cell populations, they are typically stained by a set of fluorescent reagents, e.g., antibody‐fluorophore conjugates. The number of parameters which can be studied simultaneously strongly depends on the availability of reagents which can be differentiated by their spectral properties. In this study a series of fluorescent polymer dyes was developed, that can be excited with a single violet laser (405 nm) but distinguished by their unique emission spectra. The polyfluorene‐based polymers can be used on their own, or in combination with covalently bound small‐molecule dyes to generate energy transfer constructs to red‐shift the emission wavelength based on Förster resonance energy transfer (FRET). The polymer dyes were utilized in a biological flow cytometry assay by conjugating several of them to antibodies, demonstrating their effectiveness as reagents. This report represents the first systematic investigation of structure–property relationships for this type of fluorescent dyes.
Upcycling of Carbon Fiber/Thermoset Composites into High‐Performance Elastomers and Repurposed Carbon Fibers
Authors: Yang Tiantian , Lu Xingyuan , Wang Xiaohan , Wei Xiang , An Ni , Li Yixuan , Wang Wenjie , Li Xiang , Fang Xu , Sun Junqi 
Published: March 2024

AbstractRecycling of carbon fiber‐reinforced polymer composites (CFRCs) based on thermosetting plastics is difficult. In the present study, high‐performance CFRCs are fabricated through complexation of aromatic pinacol‐cross‐linked polyurethane (PU−AP) thermosets with carbon fiber (CF) cloths. PU−AP thermosets exhibit a breaking strength of 95.5 MPa and toughness of 473.6 MJ m−3 and contain abundant hydrogen‐bonding groups, which can have strong adhesion with CFs. Because of the high interfacial adhesion between CF cloths and PU−AP thermosets and high toughness of PU−AP thermosets, CF/PU−AP composites possess a high tensile strength of >870 MPa. Upon heating in N,N‐dimethylacetamide (DMAc) at 100 °C, the aromatic pinacols in the CF/PU−AP composites can be cleaved, generating non‐destructive CF cloths and linear polymers that can be converted to high‐performance elastomers. The elastomers are mechanically robust, healable, reprocessable, and damage‐resistant with an extremely high tensile strength of 74.2 MPa and fracture energy of 149.6 kJ m−2. As a result, dissociation of CF/PU−AP composites enables the recovery of reusable CF cloths and high‐performance elastomers, thus realizing the upcycling of CF/PU−AP composites.
Enabling Closed‐Loop Circularity of “Non‐Polymerizable” α, β‐Conjugated Lactone Towards High‐Performance Polyester with the Assistance of Cyclopentadiene
Authors: Wu Xiao‐Tong , Yang Chun , Xi Jian‐Shu , Shi Changxia , Du Fu‐Sheng , Li Zi‐Chen 
Published: March 2024

AbstractChemical recycling of polymers to monomers presents a promising solution to the escalating crisis associated with plastic waste. Despite considerable progress made in this field, the primary efforts have been focused on redesigning new monomers to produce readily recyclable polymers. In contrast, limited research into the potential of seemingly “non‐polymerizable” monomers has been conducted. Herein, we propose a paradigm that leverages a “chaperone”‐assisted strategy to establish closed‐loop circularity for a “non‐polymerizable” α, β‐conjugated lactone, 5,6‐dihydro‐2H‐pyran‐2‐one (DPO). The resulting PDPO, a structural analogue of poly(δ‐valerolactone) (PVL), exhibits enhanced thermal properties with a melting point (Tm) of 114 °C and a decomposition temperature (Td,5%) of 305 °C. Notably, owing to the structural similarity between DPO and δ‐VL, the copolymerization generates semi‐crystalline P(DPO‐co‐VL)s irrespective of the DPO incorporation ratio. Intriguingly, the inherent C=C bonds in P(DPO‐co‐VL)s enable their convenient post‐functionalization via Michael‐addition reaction. Lastly, PDPO was demonstrated to be chemically recyclable via ring‐closing metathesis (RCM), representing a significant step towards the pursuit of enabling the closed‐loop circularity of “non‐polymerizable” lactones without altering the ultimate polymer structure.
Antidiabetic and antioxidant studies of novel synthesized titanium (IV) complex: Design, synthesis, in‐silico docking and in‐vitro studies
Authors: Kaushal Raj , Kaur Mandeep , Kumar Jatin , Gupta Pratiksha , Ravikant  , Sharma Jyoti 
Published: March 2024

[{TiCl3}2(C3N3S3H)] (where C3N3S3H is Trithiocyanuric acid) was designed and synthesized by the reaction of TiCl4 and trithiocyanuric acid in 2:1 M ratio under stirring and refluxing condition using THF solvent. The synthesized Titanium (IV) complex was characterized by various spectroscopic techniques like FT‐IR, NMR, MASS, XRD, UV–visible spectrophotometer and elemental analysis (CHNSO). Moreover, in‐silico docking studies of the ligand and its Ti (IV) complex were carried out by AutoDockTools‐1.5.6 to study interactions of the complex under study with the receptor protein. Afterwards, both ligand and synthesized Ti (IV)complex were screened for the antioxidant and antidiabetic potential by in‐vitro method. The antioxidant potential was investigated by using DPPH (2,2‐diphenyl‐1‐picrylhydrazyl) radical scavenging assay where ligand exhibited moderate activity while Ti (IV) complex presented significant antioxidant activity. Following, alpha‐amylase enzyme inhibition was investigated using iodine‐starch inhibition assay. It was found that the ligand was inactive (showed no α‐amylase inhibition activity) while the Ti (IV)complex was a potent α‐amylase inhibitor. Furthermore, the experimentally obtained results were also complimented by the in‐silico results.
Chemical compositions and crystallization characteristics of SOS‐rich fats
Authors: Hou Xueying , Gao Ziwei , Elbarbary Abdelaziz , Jin Jun 
Published: March 2024

AbstractSOS‐rich fats have been developed to improve heat stable properties and fat bloom‐resistant abilities of chocolates, which is highly connected with their crystallization behaviors. Shea butter stearin (SBS) and mango kernel fat (MKF) are the typical SOS‐rich fats. Both contained high levels of stearic acid (45.06%–59.67%) and oleic acid (31.85%–39.97%), while 77.00%–86.88% of the oleic acid were distributed at the sn‐2 positions of triacylglycerol molecules, contributing to forming 78.04% of SOS in SBS and 47.85% of SOS in MKF. Their SOS levels were significantly higher than that in cocoa butter (CB, 25.43%). However, MKF contained the highest levels of SOO (15.59%), which was about six to eight times as likely that in SBS and CB (1.76%–2.66%). Further crystallization tests revealed that SBS and MKF exhibited similar rod‐like growth from instantaneous nuclei at 4°C. The former was then changed to become more spherulitic growth at 20°C significantly. Specifically, large feather‐like crystals corresponding to β form were observed in SBS at the final stage of crystallization at 20 and 30°C, while MKF exhibited smaller crystals. The higher concentration of SOO in MKF was considered as the softening factor. It was further supposed that constant crystallization at 20°C may be difficult for some fats (e.g., SOS < 30%) to form adequate amounts of β crystals. The results will provide information on making cocoa butter blends and chocolate tempering.
Synthesis and characterization of foams generated via gel state frontal polymerization
Authors: Daguerre‐Bradford John , Camarda Daniel S. , Lesser Alan J. , Cristadoro Anna M. , Linnenbrink Martin , Schütte Markus 
Published: March 2024

AbstractIn conventional foams, anisotropy within the microcellular structure can only be achieved through confinement in one or more directions during the foaming process. Herein, we present a novel, versatile, and energy efficient method to create unique high‐performance foams where the anisotropy of the microcellular and the microcellular structure itself is not dictated by external confinement during the foaming process. To generate such foams, an initial crosslinked gel is first created where the crosslink density of the gel can be tuned by UV intensity and cure time. Next, the gel can be foamed while simultaneously creating a second network via radically induced cationic frontal polymerization (RICFP). In this case, the anisotropy in the foam is dictated by propagation front during the RICFP and the microcellular morphology and cell surface area are dictated by the crosslink density of the gel. These two unique qualities lead to rigid foams that can be generated from a gel without the need for confinement where the microcellular size and shape can be tuned by the crosslink density of the gel precursor. A one‐pot liquid system composed of miscible epoxies, acrylates, and chemical blowing agents (CBAs), allows for control over the foam physical, mechanical, and thermal properties with glass transition temperatures ranging from 74.7 to 125.8°C. Additionally, by patterning the crosslink density of the initial gel through controlled exposure of UV, complex microcellular structures can be formed that are not possible in conventional foaming processes. This positions gel frontal polymerization and foaming as an advanced technique to produce high performing anisotropic foams with a wide array of tunable physical, mechanical, and thermal properties.
Crystallinity and mechanical properties of polypropylene products foamed by microcellular injection molding process
Authors: Yu Shengrui , Song Senzhen , Gao Huang , Wang Kai , Xu Lei , Guo Hao , Han Wen , You Jing , Liu Zhihuan , Zhou Huamin 
Published: March 2024

AbstractMicrocellular injection molding (MIM) is a pivotal technique for lightweight molding. Polypropylene (PP) is widely used in MIM due to light weight and easy processing. The crystallinity of foamed PP products influences the load‐bearing structures and consequently mechanical properties. To address the deterioration of mechanical properties caused by internal porous structure, a novel method is proposed to regulate the crystallinity by optimizing process parameters, thereby improving mechanical properties. Wide‐angle x‐ray diffraction, mechanical testing, and melt flow simulation are applied to investigate the influence of process parameters on crystallinity and mechanical properties. Parameters are further optimized by establishing a multivariate nonlinear regression model for process parameters and crystallinity. The results show that increasing melt temperature, injection rate, mold temperature, and cooling time stimulate crystallization, enhancing strength and decreasing elongation at break. Conversely, high injection ratio of supercritical fluid obstructs crystallization, reducing strength, and increasing elongation at break. The crystallinity increases by 20.81%; the corresponding tensile, flexural, and shear strength and corresponding modulus increases by 5.39% and 10.28%, 7.60% and 18.50%, 5.00% and 11.37%, and elongation at break decreased by 5.19% through the optimization of regression model. The proposed method is feasible to upgrade the mechanical properties of foamed PP products.
3D printing of cyanate ester resins with interpenetration networks for enhanced thermal and mechanical properties
Authors: Zaman Saqlain , Favela Sergio , Herrera Nicolas E. , Gandara Alejandro , Molina Laura , Hassan Md. Sahid , Gomez Sofia Gabriela , Ramirez Jean E. Montes , Mahmud Md. Shahjahan , Martinez Ana C. , Maurel Alexis , Gan Zhengtao , MacDonald Eric , Lin Yirong 
Published: March 2024

AbstractCyanate ester (PT‐30) resin possesses exceptional thermal and mechanical properties, including high heat distortion temperature, high glass transition temperature (Tg), and outstanding mechanical characteristics. Conversely, the Tg of the homopolymer of tris(2‐hydroxyethyl)isocyanurate triacrylate (T‐acrylate) surpasses that of other acrylates. The combination of PT‐30 and T‐acrylate results in the formation of an interpenetrating polymer network (IPN) through a dual curing mechanism. Furthermore, the combination of these two polymers enables the tuning of rheology for shear thinning behavior for Ink Extrusion 3D printing technology by adjusting the amount of photoinitiator and rheological modifier. Here, 3D printable ink was formulated using PT‐30, T‐acrylate with a higher Tg, a photoinitiator, and a powdered rheological additive. The printed structures underwent a dual‐curing process involving exposure to UV light and thermal curing. Thermomechanical properties of the printed samples were characterized using dynamic mechanical analysis, thermogravimetric analysis, and tensile testing. The successful formation of an IPN structure through the polymerization of T‐acrylate and PT‐30 was observed, resulting in improved mechanical properties and an elevated Tg. The Fourier transform infrared spectroscopy analysis verified the formation of cross‐linked samples. Overall, this study demonstrates the feasibility of Ink Extrusion 3D printing, using a cyanate ester resin and tris(2‐hydroxyethyl)isocyanurate triacrylate with a dual‐curing mechanism. The enhanced mechanical properties at elevated temperatures (~80% retention of room temperature tensile strength at 200°C for sample with 70/30 wt%) and high Tg of 349 ± 3°C for printed structures shown in this study make them suitable for high‐performance structural applications in industries such as aerospace, defense, and microelectronics.
Development of crosslinked polyvinyl alcohol nanofibrous membrane for microplastic removal from water
Authors: Gopakumar Anandu Nair , Ccanccapa‐Cartagena Alexander , Bell Kati , Salehi Maryam 
Published: March 2024

AbstractThis study presents the development of an innovative nanofibrous membrane to remove microplastics (MPs) from drinking water. This membrane exhibits additional functionality in removing lead (Pb), highlighting its promising potential for utilization as a point‐of‐use (POU) device. The polyvinyl alcohol (PVA) nanofibrous membranes are crosslinked using glutaraldehyde, and their efficiencies in the removal of MPs are evaluated. The results show that crosslinking the 7 and 10 wt% PVA nanofibers increases their average diameters to 330 and 581 nm, respectively, and enhances their surface area. The treatment efficiency of crosslinked PVA fibrous media is evaluated using polyethylene (PE) (5 μm ≤d ≤ 25 μm) and polystyrene (PS) MPs (d ≤ 1 μm). The filtration efficiencies of both 7 and 10 wt% c‐PVA nanofibrous media are found to be 99.8% ± 0.1% in the removal of PE MPs at pH 8. Further examination of the filtration efficiency in the removal of PS MPs shows that the highest removal efficiency achieved was 77.3% ± 1.4% at a pH of 6. Additionally, the lead removal efficiency of this fibrous membrane in flow‐through experiments is examined. Results show a pH‐dependent lead removal efficiency, in which the greatest efficiency of 69% is found at pH 6.
New perspectives on poly(lauryllactam) PA12: Optimization of process parameters for AROP of ω‐lauryllactam
Authors: Hamou Karima Ben , Bruning Ralf , LaPlante Gabriel , Thibault Marie‐Hélène , Robichaud Jacques , Djaoued Yahia 
Published: March 2024

AbstractThis study focuses on how catalyst concentration, activator concentration, and initial polymerization temperature impact in‐situ anionic ring‐opening polymerization (AROP) of ω‐lauryllactam. Catalyst and activator roles are fulfilled by NaH and toluene‐2,4‐diisocyanate (TDI), respectively, with varying catalyst/activator ratios to assess the influence of a bifunctional activator on the polymerization process. The materials produced undergo a thorough analysis, with a specific emphasis on solidification time. The examination extends to scrutinizing how different concentrations of catalyst/activator and polymerization temperatures affect crucial physical and chemical parameters. The study identifies NaH‐6 mol%/TDI‐3 mol% as the optimal formulation for solidification among the three explored temperatures. Notably, at 180 and 200°C, PA12 exhibits enhanced monomer conversion when a catalyst/activator ratio of 1.7 or 2 is applied. These findings underscore the significant impact of the catalyst/activator ratio and their individual concentrations on the polymer's final properties. This influence extends to factors such as crystallinity, polymer chain regularity, and dynamic mechanical properties. Additionally, the experimental conditions utilized for anionic polymerization are observed to shape the characteristics of PA12.