Chemical Science最新文献_第7页

Adaptive nitrogen-containing buckybowl: a versatile receptor for curved and planar aromatic molecules.

IF 7.6 1区化学

Chemical Science Pub Date : 2025-03-25 DOI: 10.1039/d5sc00988j

Xu-Lang Chen, Si-Qian Yu, Zi-You Zheng, Zhao-Yi Cheng, An-Na Chen, Jia-Qi Liang, Xin Sun, Chunyang Zheng, Xiaohuan Huang, Han-Yuan Gong

{"title":"Adaptive nitrogen-containing buckybowl: a versatile receptor for curved and planar aromatic molecules.","authors":"Xu-Lang Chen, Si-Qian Yu, Zi-You Zheng, Zhao-Yi Cheng, An-Na Chen, Jia-Qi Liang, Xin Sun, Chunyang Zheng, Xiaohuan Huang, Han-Yuan Gong","doi":"10.1039/d5sc00988j","DOIUrl":"10.1039/d5sc00988j","url":null,"abstract":"Bowl-shaped polycyclic aromatic hydrocarbons (PAHs), or buckybowls, are renowned for their unique structures and physicochemical properties, making them promising fragments for functional materials. While well-known examples like corannulene and sumanene demonstrate their potential, synthetic challenges have limited the development of other fullerene fragments. Recent advancements, particularly the incorporation of heteroatoms, have expanded the structural diversity of buckybowls. In this study, we report the synthesis of a novel nitrogen-containing buckybowl (1) using the core-periphery strategy that connects two half-bowls via a single carbon-carbon bond, followed by peripheral stitching. This molecule features two nitrogen atoms within its bowl-shaped framework, representing a significant advancement in structural diversity. Compound 1 exhibits intense red emission with high color purity and quantum yield in solution. Additionally, it possesses adaptive curvature adjustment and shows excellent binding affinity to the curved PAH corannulene, the spherical PAH C60, as well as the planar PAH pyrene. These versatile assembly capabilities highlight its potential applications in supramolecular chemistry and materials science, paving the way for advancements in molecular electronics and photonics.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11955802/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143763287","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Histidine-rich enantiomeric peptide coacervates enhance antigen sequestration and presentation to T cells.

IF 7.6 1区化学

Chemical Science Pub Date : 2025-03-25 DOI: 10.1039/d5sc01163a

Ushasi Pramanik, Anirban Das, Elise M Brown, Heather L Struckman, Huihao Wang, Samuel Stealey, Macy L Sprunger, Abdul Wasim, Jonathan Fascetti, Jagannath Mondal, Jonathan R Silva, Silviya P Zustiak, Meredith E Jackrel, Jai S Rudra

{"title":"Histidine-rich enantiomeric peptide coacervates enhance antigen sequestration and presentation to T cells.","authors":"Ushasi Pramanik, Anirban Das, Elise M Brown, Heather L Struckman, Huihao Wang, Samuel Stealey, Macy L Sprunger, Abdul Wasim, Jonathan Fascetti, Jagannath Mondal, Jonathan R Silva, Silviya P Zustiak, Meredith E Jackrel, Jai S Rudra","doi":"10.1039/d5sc01163a","DOIUrl":"10.1039/d5sc01163a","url":null,"abstract":"Peptides and peptidomimetics that self-assemble through LLPS have recently emerged as vital building blocks for creating functional biomaterials, thanks to their unique physicochemical properties and dynamic nature. One of life's most distinctive features is its selectivity for chiral molecules. To date, coacervates comprised of d-amino acids have not been reported. Here, we demonstrate that histidine-rich repeats of (GHGXY)4 (X = L/V/P) and their enantiomers undergo LLPS, paving the way for improved coacervate stability. Through a series of biophysical studies, we found that the droplet size can be tuned based on L, V, or P substitution, and molecular cargo between 600 and 150 000 Da is efficiently recruited in a bioactivity-preserving aqueous environment during phase separation. Mechanistic studies reveal that the droplets enter cells via energy-dependent endocytic pathways, exhibit composition-selective fusion properties, and effectively deliver molecular therapeutics across various cell types. Finally, we demonstrate that the coacervates enhance antigen presentation to CD4+ and CD8+ T cells, resulting in robust proliferation and the production of functional cytokines. Our study outlines the development and characterization of enantiomeric peptide coacervates as promising vaccine delivery vehicles with tunable physicochemical properties.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11955804/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143763312","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Diastereoselective 1,3-nitrooxygenation of bicyclo[1.1.0]butanes.

IF 7.6 1区化学

Chemical Science Pub Date : 2025-03-25 DOI: 10.1039/d4sc08753d

Anirban Maity, Kuruva Balanna, Constantin G Daniliuc, Armido Studer

引用次数: 0

Enhanced blue phosphorescence in platinum acetylide complexes via a secondary heavy metal and anion-controlled aggregation.

IF 7.6 1区化学

Chemical Science Pub Date : 2025-03-25 DOI: 10.1039/d5sc00172b

Vinh Q Dang, Chenggang Jiang, Thomas S Teets

{"title":"Enhanced blue phosphorescence in platinum acetylide complexes via a secondary heavy metal and anion-controlled aggregation.","authors":"Vinh Q Dang, Chenggang Jiang, Thomas S Teets","doi":"10.1039/d5sc00172b","DOIUrl":"10.1039/d5sc00172b","url":null,"abstract":"Organoplatinum compounds represent a promising class of blue-phosphorescent molecules for electroluminescent color displays. Much recent work has focused on decreasing the nonradiative rate constant (k nr) to improve the photoluminescence quantum yield (Φ PL) of these compounds, but in most cases small radiative rate constants (k r) lead to long excited-state lifetimes (τ) poorly suited for electroluminescence applications. In this work, we present an approach to increase k r and Φ PL in blue-phosphorescent platinum acetylide complexes with the general formula cis-[Pt(CN-R)2(C[triple bond, length as m-dash]C-2-py)2] (CN-R is an alkyl isocyanide and C[triple bond, length as m-dash]C-2-py is 2-pyridylacetylide). This method incorporates secondary heavy metals, Cu(i) or Ag(i), bound by the pyridyl moieties. We observe the formation of dimer complexes in the solid state due to noncovalent interactions between the secondary metal and the acetylide ligands, especially strong in the case of Cu(i). Incorporation of Cu(i) also erodes the desired blue-phosphorescence by introducing a low-lying metal-to-ligand charge transfer (3MLCT) state that dominates the observed phosphorescence. In the complexes bound to Ag(i), we find that phosphorescence profile is strongly dependent on the counteranion, which we propose is caused by different degrees of aggregation. With this insight, we show that coordination of AgBArF 4 (BArF 4 - = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate), with a large noncoordinating counteranion, inhibits aggregation and results in a 4-8× increase in k r and a 5-10× increase in Φ PL while preserving a pure blue phosphorescence profile.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11934150/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143718185","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ultra-low concentration ether electrolytes with strong Coulomb interactions for high-voltage lithium metal batteries.

IF 7.6 1区化学

Chemical Science Pub Date : 2025-03-25 DOI: 10.1039/d4sc07393b

Chengkun Liu, Zhipeng Jiang, Yuhang Zhang, Wenjun Xie, Jiahang Zou, Shilin Wu, Mengjun Sun, Yongtao Li

{"title":"Ultra-low concentration ether electrolytes with strong Coulomb interactions for high-voltage lithium metal batteries.","authors":"Chengkun Liu, Zhipeng Jiang, Yuhang Zhang, Wenjun Xie, Jiahang Zou, Shilin Wu, Mengjun Sun, Yongtao Li","doi":"10.1039/d4sc07393b","DOIUrl":"https://doi.org/10.1039/d4sc07393b","url":null,"abstract":"The advancement of high-energy-density lithium metal batteries (LMBs) necessitates the development of novel electrolytes capable of withstanding high voltages. Ether-based electrolytes, while compatible with lithium metal anodes (LMAs), face limitations in high-voltage stability. Traditional design strategies with high concentration enhance the high-voltage stability of electrolytes by consuming free solvents to prevent their decomposition but face high-cost issues. Herein, we introduce a novel design approach for high-voltage ether electrolytes that leverages strong Coulomb interactions between lithium ions (Li+) and anions to construct an anion-dominated solvation structure. This solvation structure not only enhances de-solvation kinetics but also forms stable anion-derived interfaces at both electrodes, thereby maintaining electrode stability and preventing free solvent decomposition. Li-LiNi0.8Co0.1Mn0.1O2 (NCM811) cells using a strong Coulomb force electrolyte (SCE) designed based on this principle demonstrate superior rate performance (20C/120.8 mA h g-1) and cycling stability (5C/1000 cycles). Notably, even at an ultra-low concentration of 0.1 M, Li-NCM811 cells utilizing the SCE exhibit good rate performance (5C/121.9 mA h g-1) and stable cycling over 200 cycles at a cutoff voltage of 4.4 V. This approach provides a high-performance and cost-effective electrolyte solution for practical high-voltage LMB applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11959740/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143771535","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The role of structural defects in the fluoride-mediated synthesis of aluminosilicate zeolites.

IF 7.6 1区化学

Chemical Science Pub Date : 2025-03-25 DOI: 10.1039/d5sc00899a

Kingsley Christian Kemp, Ömer F Altundal, Donghui Jo, Weidong Huang, Qiang Wang, Feng Deng, German Sastre, Suk Bong Hong

{"title":"The role of structural defects in the fluoride-mediated synthesis of aluminosilicate zeolites.","authors":"Kingsley Christian Kemp, Ömer F Altundal, Donghui Jo, Weidong Huang, Qiang Wang, Feng Deng, German Sastre, Suk Bong Hong","doi":"10.1039/d5sc00899a","DOIUrl":"10.1039/d5sc00899a","url":null,"abstract":"The existence of framework defects in zeolites, an important class of industrial catalysts and adsorbents, has long been recognized, but little is known about their exact role in zeolite crystallization. Here we show that despite their relatively high framework Al content (Si/Al = 11.5-13.8), as-synthesized PWO, PWW and RTH zeolites, obtained using various trimethylpyridinium cation isomers as organic structure-directing agents (OSDAs) in concentrated fluoride media, contain unexpectedly large amounts of SiO-···HOSi defects which counterbalance the charge of 11-39% of the total OSDA cations occluded per unit cell, but have only a negligible amount (<0.1 ions per unit cell) of fluoride anions. The results suggest that the phase selectivity of the crystallization in the presence of fluoride ions may be determined by a combination of Al incorporation into the silicate framework, the type of OSDAs used and the microstructure and concentration of SiO-···HOSi defects formed. This study provides a new basis for better understanding the fundamental aspects of zeolite crystallization mechanisms.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11956030/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143762538","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Umpolung of a covalent organic framework for high-performance cathodic sodium ion storage.

IF 7.6 1区化学

Chemical Science Pub Date : 2025-03-25 DOI: 10.1039/d5sc01195g

Fangyuan Kang, Yuchan Zhang, Zihao Chen, Zhaowen Bai, Qianfeng Gu, Jinglun Yang, Qi Liu, Yang Ren, Chun-Sing Lee, Qichun Zhang

{"title":"Umpolung of a covalent organic framework for high-performance cathodic sodium ion storage.","authors":"Fangyuan Kang, Yuchan Zhang, Zihao Chen, Zhaowen Bai, Qianfeng Gu, Jinglun Yang, Qi Liu, Yang Ren, Chun-Sing Lee, Qichun Zhang","doi":"10.1039/d5sc01195g","DOIUrl":"https://doi.org/10.1039/d5sc01195g","url":null,"abstract":"The rational design of electrode materials to modify their intrinsic electronic states effectively enhances the performance of rechargeable batteries. Herein, an umpolung strategy is implemented in preparing a polyimide-linked COF (CityU-47) through a polar inversion of the typical p-type triphenylamine (TPA) with a multi-carbonyl-contained n-type azatriangulenetrione (ATTO). This strategy can substantially decrease the energy level of the lowest unoccupied molecular orbital (LUMO), thereby increasing the potential for operation as a cathode material. Alongside increased specific capacity, an improved overall performance in sodium-ion batteries (SIBs) is achieved. Specifically, CityU-47 provides a high capacity of 286.31 mA h g-1 at a current density of 0.1 A g-1, and a cycle capacity of 210 mA h g-1 at 2 A g-1 over 1800 cycles is also achieved. This research offers fresh perspectives on enhancing battery performance, underscoring the importance of regulating electron structures at the atomic level.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11960781/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143771539","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Distinctive signatures and ultrafast dynamics of Brønsted sites, silanol nests and adsorbed water in zeolites revealed by 2D-IR spectroscopy.

IF 7.6 1区化学

Chemical Science Pub Date : 2025-03-25 DOI: 10.1039/d4sc08093a

Paul M Donaldson, Alexander P Hawkins, Russell F Howe

{"title":"Distinctive signatures and ultrafast dynamics of Brønsted sites, silanol nests and adsorbed water in zeolites revealed by 2D-IR spectroscopy.","authors":"Paul M Donaldson, Alexander P Hawkins, Russell F Howe","doi":"10.1039/d4sc08093a","DOIUrl":"10.1039/d4sc08093a","url":null,"abstract":"Characterising hydroxyl groups in zeolites and other amorphous solids often relies on methods such as IR and NMR spectroscopy. Their power to distinguish different types of hydroxyl groups diminishes when band broadening from hydrogen bonding and structural heterogeneity occurs. In support of this problem, we report in situ femtosecond 2D-IR spectroscopy of some of the different types of hydroxyl groups present in zeolites. Despite the samples studied being optically scattering pellets, we show that their structural and rotational dynamics can be determined. We show that the hydroxyl groups of Brønsted acid sites, silanol defects and water of hydration display distinct features in their 2D-IR spectra. Brønsted site hydroxyl group structural distributions have characteristic inhomogeneously broadened 2D-IR bandshapes. Water of hydration and partially hydrogen bonded silanol groups give unique 2D-IR cross peak signatures off-diagonal. Hydrogen bonded silanol groups arising from vacancy defects (silanol nests) show a distinctive 2D-IR signature with unique ultrafast dynamics observed to be identical between ZSM-5 and silicalite-1. 2D-IR spectroscopy makes IR measurements quantitative, and we use this property to estimate the concentration of ZSM-5 silanol nest hydroxyl groups relative to the number of Brønsted sites. Overlapping silanol nest spectral features are revealed by frequency dependence of their vibrational lifetime. In contrast to other framework hydroxyls, the silanol nest band shows picosecond 2D-IR anisotropy decay and spectral diffusion. The signatures of nest structural mobility revealed here presents new opportunities to understand these hitherto elusive structural defects.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11935784/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143718175","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Minimal Catalytic Dissipative Assemblies via Cooperation of Amino acid, Nucleobase precursor and Cofactor

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-24 DOI: 10.1039/d5sc00827a

Syed Pavel Afrose, Soumili Roy, Pratip Bhattacharya, Ajeet Kumar Singh, Lisa Roy, Dibyendu Das

{"title":"Minimal Catalytic Dissipative Assemblies via Cooperation of Amino acid, Nucleobase precursor and Cofactor","authors":"Syed Pavel Afrose, Soumili Roy, Pratip Bhattacharya, Ajeet Kumar Singh, Lisa Roy, Dibyendu Das","doi":"10.1039/d5sc00827a","DOIUrl":"https://doi.org/10.1039/d5sc00827a","url":null,"abstract":"Functions arising from cooperation between protobiopolymers fueled the chemical emergence of living matter that requires continuous supply of energy to exist in a far-from-equilibrium state. Non-equilibrium conditions imparted by available energy sources played critical roles in the appearance of complex co-assembled architectures which exploited the properties of different classes of biopolymers. Such co-assemblies formed from mixtures of nitrogenous heterocycles as protonucleobases and peptide precursors might have acted as early versions of catalytic machinery capable of sustaining chemical reaction networks. Herein, we show the generation of catalytic non-equilibrium networks from a mixture of a nitrogenous heterocycle, an amino acid and a cofactor driven by an aromatic substrate. The cooperation, a result of supramolecular interactions between different components rendered the assemblies capable of activating the cofactor towards oxidative degradation of the substrate which resulted in autonomous disassembly (negative feedback). Further, utilising a promiscuous hydrolytic capability, the transient co-assemblies could metabolise a precursor to generate additional amounts of the substrate which enhanced the lifetime (positive feedback) of the assemblies.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"46 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677664","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Graphendofullerene: a novel molecular two-dimensional ferromagnet

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-24 DOI: 10.1039/d5sc01278c

Diego López-Alcalá, Ziqi Hu, José J. Baldoví

引用次数: 0