化学•材料最新文献

{"title":"Paramagnetic Gas Adsorbed in Metal–Organic Framework: A Promising Platform for Spin Qubits Design","authors":"Anastasiya A. Yazikova, Aleksandr S. Tomilov, Nikita A. Afimchenko, Igor L. Zilberberg, Anatoly R. Melnikov, Kristina A. Smirnova, Artem S. Poryvaev, Matvey V. Fedin","doi":"10.1021/acs.jpcc.5c01670","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01670","url":null,"abstract":"Development of viable quantum bits (qubits) is currently among the main challenges in quantum technologies. One approach to this problem that utilizes the potential of synthetic chemistry is the creation of molecular spin qubits (MSQs). Metal–organic frameworks (MOFs) are promising materials for scaling up MSQ systems while also exhibiting useful sorption properties. We report the adsorption of paramagnetic nitric oxide (NO) in MOF-808 and its modifications and for the first time propose an adsorbed “gas@MOF” concept to design MSQs. Continuous-wave electron paramagnetic resonance (CW EPR) allowed monitoring of the NO adsorption process that occurs at temperatures below 150 K and leads to immobilization of NO molecules within the MOF-808 matrix. Electron decoherence times <i>T</i>_m acquired by pulse EPR were found sufficiently long to perform simple spin manipulations (∼1.5 μs), which was demonstrated by a Rabi-oscillation experiment. Thus, gas molecules adsorbed in MOFs, “gas@MOF”, can act as potential spin qubits, as was exemplified by NO@MOF-808 as a proof of principle, and can be further extended to other paramagnetic gases and various MOFs.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"58 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841873","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Iron-Catalyzed Thioarylation of Arenes Using Saccharin-Derived Reagents","authors":"Lachlan J. N. Waddell, Oluwajuwon A. M. Okunade, Amy C. Dodds, Michael C. H. Lok, R. Nisha Khanizeman, Andrew Sutherland","doi":"10.1021/acs.joc.5c00250","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00250","url":null,"abstract":"Biaryl sulfides are important scaffolds found in various natural products and pharmaceutically active compounds. One of the main approaches for the synthesis of this compound class involves the substitution of arenes using electrophilic thioaryl species. However, these methods generally require acidic activation of the electrophile, more forcing conditions, and long reaction times. Here, we describe the combination of the super Lewis acid iron(III) triflimide with saccharin-based thioarylation reagents for the rapid synthesis of unsymmetrical biaryl sulfides under mild conditions. This approach was effective with electron-deficient thioaryl species that performed poorly with previous methods, allowing the efficient functionalization of bioactive compounds.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"29 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841986","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"High-Pressure X-ray Diffraction Investigation of Fe0.9Al0.1VO4","authors":"Vinod Panchal, Pablo Botella, Neha Bura, Frederico G. Alabarse, Enrico Bandiello, Marco Bettinelli, Daniel Errandonea","doi":"10.1021/acs.jpcc.5c01418","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01418","url":null,"abstract":"This study demonstrates that the influence of cationic composition on the phase behavior of vanadates under high pressure must be meticulously considered. In this investigation, we report an in situ high-pressure powder X-ray diffraction investigation on triclinic Fe_0.9Al_0.1VO₄ (space group <i>P</i>1̅) up to 11 GPa. The structural sequence of Fe_0.9Al_0.1VO₄ is different than that of FeVO₄. Our analysis shows that Fe_0.9Al_0.1VO₄ undergoes a first-order structural phase transition at 2.85 GPa to another triclinic structure described by the same space group with a volume collapse of ∼9%. At 6.1 GPa, we observed the onset of a second phase transition to a monoclinic structure (space group <i>P</i>2/<i>c</i>), with coexistence of both phases until 8.55 GPa. The transformation to the second phase is completed at 9.15 GPa, with a volume collapse of ∼13%. On release of pressure to ambient conditions, we have observed the coexistence of the second and first high-pressure phases. The compressibility of the three phases of the compound has been studied too. We have observed variations in structural sequence and compressibility behavior due to Al incorporation. Since electronic properties could be modified by tuning the crystal structure, the present results could have an impact on applications of the studied compound such as photocatalysis and batteries.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"20 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841871","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Sulfonated covalent organic frameworks (COF)/polyethersulfone (PES) membrane with enhanced hemocompatibility for blood oxygenation","authors":"Yue Huang ,&nbsp;Lunhao Zhi ,&nbsp;Chong Cheng ,&nbsp;Qiang Wei ,&nbsp;Shudong Sun ,&nbsp;Changsheng Zhao","doi":"10.1016/j.colsurfb.2025.114716","DOIUrl":"10.1016/j.colsurfb.2025.114716","url":null,"abstract":"<div><div>In extracorporeal membrane oxygenation (ECMO) treatment, designing membrane with self-anticoagulant properties can solve problems resulting from the adverse effect of anticoagulants. In this study, 2,4,6-Triformylphloroglucinol (Tp) and 2,5-Diaminobenzenesulfonic acid (Pa-SO₃H) were applied to grow a sulfonated COF film in situ on the polyethersulfone (PES) membrane. The introduction of sulfonic groups increased the hydrophilicity and electronegativity of the TpPa COF film, improved its anti-protein adhesion properties, maintained the normal morphology of blood cells, and endowed the COF film with antithrombotic properties. In the porcine blood circulation test, the duration to increase So₂ (O₂ saturation) from ∼75–95 % in TpPa-SO₃H COF/PES membrane (M-TpPa-SO₃H) was 70 min shorter than that in TpPa COF/PES membrane (M-TpPa). This preparation method is applicable to the preparation of not only flat membranes, but also hollow fiber membranes. These findings emphasize the potential of M-TpPa-SO₃H in ECMO applications, providing superior antithrombotic property and CO₂ efflux potential.</div></div>","PeriodicalId":279,"journal":{"name":"Colloids and Surfaces B: Biointerfaces","volume":"253 ","pages":"Article 114716"},"PeriodicalIF":5.4,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143844460","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Emissions of HFC-134a in China and Reconciliation of Discrepancies between Observation-Based and Inventory-Based Emission Estimates","authors":"Mengyue Ma, Bo Yao, Xiaoyi Hu, Bowei Li, Wenxue Chi, Di Chen, Liting Hu, Guus J. M. Velders, Xuekun Fang","doi":"10.1021/acs.est.5c02636","DOIUrl":"https://doi.org/10.1021/acs.est.5c02636","url":null,"abstract":"HFC-134a (1,1,1,2-tetrafluoroethane) is a potent greenhouse gas with global warming potential thousands of times larger than that of carbon dioxide (CO₂). HFC-134a is regulated under the Montreal Protocol. However, the emissions, consumption, and emission–consumption relationships of HFC-134a are unclear. Here, this study reveals that observation-based HFC-134a emissions increased from 19.5 ± 2.5 Gg yr^–1 in 2011 to 33.1 ± 7.5 Gg yr^–1 in 2020 in China, but with a lower increase (2%) compared to those (48%) reported in a previous inventory-based emission estimate from 2015 to 2020. Consequently, the emission discrepancy between observation-based and inventory-based emissions reached 24.9 ± 7.5 Gg yr^–1 (equivalent to 36.6 ± 11.0 Tg of CO₂-eq yr^–1) in 2020. Therefore, this study built a novel approach (Observation-based Sectoral Activity and Emission Function Attribution Model, OSAM) to quantitatively attribute these emission discrepancies. We found that the emission discrepancies of HFC-134a were generally attributed to the consumption (35.6%) and emission functions (64.4%) used in previous emission inventories; thereby an emission inventory with new emission–consumption relationships, which matched the observation-based estimates, was established in this study. This study provides an emission discrepancy reconciliation approach applicable worldwide.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"42 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841145","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Solvent-Controlled and Highly Chemoselective Reduction of α,β-Unsaturated Ketones and Aldehydes","authors":"Yu-kun Zhang, Eman Fayad, Hanadi A. Katouah, Hua-Li Qin","doi":"10.1021/acs.joc.5c00151","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00151","url":null,"abstract":"Herein, we establish two highly efficient reductions of α,β-unsaturated ketones and aldehydes via Raney nickel-catalyzed hydrogenation with distinct chemoselectivity, which is controlled by the solvent. This methodology demonstrates a brilliant result when reducing α,β-unsaturated ketones and aldehydes to ketones or alcohols. High isolated yields were obtained for a series of benzalacetone- and cinnamaldehyde-derived substrates without additional column chromatographic purification. The practicability of the methodology was demonstrated by reducing the natural products and synthesizing the approved drug.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"37 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841987","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dietary Diversity Modified the Association of Per- and Polyfluoroalkyl Substances with Accelerated Biological Aging: Evidence from the China National Human Biomonitoring Study","authors":"Zheng Zhang, Nan Sheng, Yingli Qu, Zhanhong Xue, Feng Zhao, Bing Wu, Chunxian Lv, Fengfeng Dong, Jinghua Wang, Haocan Song, Qi Sun, Miao Zhang, Fanye Long, Yawei Li, Saisai Ji, Zheng Li, Xu Zhang, Hui Fu, Kexin Li, Jiayi Cai, Ying Zhu, Zhaojin Cao, Shilu Tong, Yuebin Lv, Jiayin Dai, Yitao Pan, Xiaoming Shi","doi":"10.1021/acs.est.4c13048","DOIUrl":"https://doi.org/10.1021/acs.est.4c13048","url":null,"abstract":"Per- and polyfluoroalkyl substances (PFASs) can impact various systems in the human body. However, their influence on biological aging remains unclear. This study aims to investigate the association between PFASs exposure and biological aging based on data from 9756 participants in the China National Human Biomonitoring Program and assesses the potential moderating effect of Dietary Diversity Score (DDS). Biological age indexes were calculated using the Klemera–Doubal method (KDM) and Mahalanobis distance (MD). The DDS was calculated based on the consumption frequency of 13 food groups over the past 12 months. Most PFASs showed positive associations with KDM-age acceleration (KDM-AA), while no statistically significant associations were observed with MD. The dose–response relationships of PFASs with KDM-AA and MD were steeper at low concentrations of PFASs, and then the slope appeared flat at higher concentrations. The weighted quantile sum revealed positive mixture effects of PFASs on biological aging. PFHpS and PFNA were both major contributors to KDM-AA and MD. DDS appeared to potentially modify the association between PFASs and biological aging. Our findings demonstrate that PFASs were significantly associated with accelerated biological aging, whereas higher DDS mitigates these adverse effects, highlighting the importance of this preventive measure.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"17 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837606","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Biobased self-healing functional composites and their applications","authors":"Elham Nadim,&nbsp;Ian Major,&nbsp;Declan Devine,&nbsp;Pavan Paraskar","doi":"10.1186/s42252-025-00065-x","DOIUrl":"10.1186/s42252-025-00065-x","url":null,"abstract":"<div><p>Self-healing composites are innovative materials designed to autonomously repair damage and restore functionality, offering a sustainable alternative to traditional thermosetting materials. These materials enable self-repair without external intervention, extending service life and reducing maintenance costs. Recently, bio-based self-healing composites comprising matrices and fillers derived from renewable resources such as polysaccharides (e.g., cellulose), lignin, vegetable oils, and vanillin have emerged as a promising solution to reduce dependence on non-renewable petroleum-based materials. This review delves into the advancements in bio-based self-healing composites, with a focus on systems utilizing dynamic covalent bonds (e.g., hydroxyl ester, Schiff base, disulfide bonds) and dynamic non-covalent interactions. It explores diverse self-healing mechanisms, including supramolecular chemistry, covalent bond reformation, diffusion and flow, heterogeneous systems, and shape-memory effects, as well as their synergistic combinations. The discussion spans both physical and chemical approaches, highlighting integrated physico-chemical strategies. Furthermore, the review examines state-of-the-art fabrication techniques and the broad range of applications for these materials. Future perspectives and research directions underscore the pivotal role of bio-based self-healing composites in advancing sustainable and durable solutions across multiple industries.</p></div>","PeriodicalId":576,"journal":{"name":"Functional Composite Materials","volume":"6 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://jmscomposites.springeropen.com/counter/pdf/10.1186/s42252-025-00065-x","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143835710","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Low-velocity impact response of carbon/epoxy laminates with interlaminar hybrid toughening via core–shell-rubber particles and non-woven thermoplastic fibre veils","authors":"Mehmet Çağatay Akbolat ,&nbsp;Sheng Wang ,&nbsp;Kali Babu Katnam ,&nbsp;Prasad Potluri ,&nbsp;Constantinos Soutis","doi":"10.1016/j.compositesa.2025.108944","DOIUrl":"10.1016/j.compositesa.2025.108944","url":null,"abstract":"<div><div>Advanced composites (<em>e.g.</em> carbon fibre-reinforced epoxies) have been increasingly used in lightweight, critical applications such as aerospace, renewable energy and defence industries due to their excellent mechanical properties including high specific strength, stiffness and fatigue properties. However, the inherent brittleness of polymer composites makes them vulnerable to low-velocity out-of-plane impact loading, threatening their structural integrity. In this context, enhancing the low-velocity impact resistance of composite laminates is crucial for maintaining their structural integrity and reliability throughout their service life. Therefore, this study explores the low-velocity out-of-plane impact resistance of composite laminates (<em>i.e.</em> consisting of the unidirectional non-crimp carbon fibre fabrics and low-viscous two-part epoxy resin) toughened with core–shell rubber (CSR) particles and thermoplastic veils. The CSR particles varying from 0.1 to 3µm and Polyphenylene Sulfide (PPS) fibre veils with a fibre diameter of <span><math><mrow><mspace></mspace><mn>9</mn></mrow></math></span> µm were used to achieve non-hybrid and hybrid toughening. The impact response of the composite laminates, manufactured with vacuum-assisted resin infusion and out-of-autoclave curing, were characterised with drop-weight low-velocity impact testing in two energy ranges: near the delamination threshold (<em>i.e.</em> 2 J, 3 J, 4 J) and over a broader range (<em>i.e.</em> 2.5 J, 5 J, 7.5 J, 10 J). The results show that the toughening mechanisms derived from the hybrid use of PPS veils and CSR particles effectively enhance the impact resistance of composite laminates up to the delamination threshold. Additionally, the hybrid approach significantly reduces the projected damage area. However, beyond the delamination threshold, the influence of these toughening mechanisms on the impact properties is found to be limited.</div></div>","PeriodicalId":282,"journal":{"name":"Composites Part A: Applied Science and Manufacturing","volume":"195 ","pages":"Article 108944"},"PeriodicalIF":8.1,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143843547","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Livestock–Crop–Mushroom (LCM) Circular System: An Eco-Friendly Approach for Enhancing Plant Performance and Mitigating Microbiological Risks","authors":"Dong Liu, Yousif Abdelrahman Yousif Abdellah, Tingting Dou, Katharina Maria Keiblinger, Ziyan Zhou, Parag Bhople, Jishao Jiang, Xiaofei Shi, Fengming Zhang, Fuqiang Yu, Baoshan Xing","doi":"10.1021/acs.est.4c12517","DOIUrl":"https://doi.org/10.1021/acs.est.4c12517","url":null,"abstract":"Mushroom production using agroforestry biowaste is a great green cycling agriculture alternative. Therefore, the current study explored the Livestock–Crop–Mushroom (LCM) circular production model, starting with co-composting of straw and cow manure as a’St’ biofertilizer further used for mushroom cultivation that ultimately produced a’StM’ biofertilizer. The two biofertilizers were tested for their impacts on plant growth and potential microbial risks. The results show significant growth of oats stimulated by biofertiliser use. Both’St’ and’StM’ increased plant biomass, while with the latter, the crude protein content (+5.1%) and root biomass were also higher. Reduced abundances of resistome genes (30%) and pathogens (25%) were observed during the oat growth. Further, metagenomics analysis also indicated a reduction in antibiotic-resistance genes by −20% in soils with oats treated by’St’ and −46% in’StM’ biofertilizer treatment. The’StM’ had a three-fold stronger inhibitory effect on oat rhizosphere soil pathogens than’St’. Moreover, compared to’St’,’StM’ suppressed pathogens in seeds and stems, with specific beneficial biomarker microbes in different plant parts. Overall, the antibiotic resistance gene related to oxytetracycline decreased more than three-fold in the LCM system. This study demonstrates the substantial potential and scalability of the LCM circular system within the agricultural domain.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"22 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841139","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}