Chemical Science最新文献_第5页

Controlling the spatial distribution of electronic excitation in asymmetric D-A-D’ and symmetric D’-A-D-A-D'

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-04 DOI: 10.1039/d5sc01257k

Evangelos Balanikas, Tommaso Bianconi, Pietro Mancini, Nikhil Tewari, Manju Sheokand, Rajneesh Misra, benedetta. carlotti, Eric Vauthey

{"title":"Controlling the spatial distribution of electronic excitation in asymmetric D-A-D’ and symmetric D’-A-D-A-D'","authors":"Evangelos Balanikas, Tommaso Bianconi, Pietro Mancini, Nikhil Tewari, Manju Sheokand, Rajneesh Misra, benedetta. carlotti, Eric Vauthey","doi":"10.1039/d5sc01257k","DOIUrl":"https://doi.org/10.1039/d5sc01257k","url":null,"abstract":"Understanding how electronic energy is funnelled towards a specific location in a large conjugated molecule is of primary importance for the development of a site-specific photochemistry. To this end, we investigate here how electronic excitation redistributes spatially in a series of electron donor-acceptor (D-A) molecules containing two different donors, D and D', and organised in both linear D-A-D' and symmetric double-branch D'-A-D-A-D' geometries. Using transient IR absorption spectroscopy to probe the alkyne spacers, we show that for both types of systems in non-polar solvents, excitation remains delocalised over the whole molecule. In polar media, charge-transfer (CT) exciton in the linear D-A-D' systems localises rapidly at the end with the strongest donor. For the double-branch systems, excited-state symmetry breaking occurs and the CT exciton localises at the end of one of the two branches, even if the D' terminal donor is not the strongest one. This unexpected behaviour is explained by considering that the energy of a CT state depends not only on the electron donating and withdrawing properties of the donor and acceptor constituents, but also on the solvation energy. This study demonstrates the possibility to control the location of CT excitons in large conjugated systems by varying the nature of the donors and acceptors, the distance between them as well as the environment.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"108 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775906","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

Insights into Topochemical versus Stress-Induced High-Pressure Reactivity of Azobenzene by Single Crystal X-ray Diffraction

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-04 DOI: 10.1039/d5sc00432b

Milo Agati, Sebastiano Romi, Samuele Fanetti, Krzysztof Radacki, Hanfland Michael, Holger Braunschweig, Todd B Marder, Stewart Clark, Alexandra Friedrich, ROBERTO BINI

{"title":"Insights into Topochemical versus Stress-Induced High-Pressure Reactivity of Azobenzene by Single Crystal X-ray Diffraction","authors":"Milo Agati, Sebastiano Romi, Samuele Fanetti, Krzysztof Radacki, Hanfland Michael, Holger Braunschweig, Todd B Marder, Stewart Clark, Alexandra Friedrich, ROBERTO BINI","doi":"10.1039/d5sc00432b","DOIUrl":"https://doi.org/10.1039/d5sc00432b","url":null,"abstract":"This study addresses azobenzene's structural compression and reactivity under hydrostatic high-pressure conditions. Synchrotron X-ray diffraction data of single crystals compressed with neon as the pressure-transmitting medium allowed the refinement of the crystal structure up to 28 GPa, at which the onset of the reaction was observed. Analysis of the pressure-dependent lattice parameters reveals a first-order isostructural phase transition at 13 GPa. We have solved the crystal structure of the high-pressure phase of azobenzene offering a key insight into the strong contribution of stress on the structural compression mechanism and crystal's reaction chemistry at elevated pressures. While the collapse of the b cell parameter, previously observed under non-hydrostatic conditions, was identified as the crucial step toward the formation of azobenzene-derived double-core nanothreads, under quasi-hydrostatic conditions the compression of the cell parameters up to 33 GPa followed a different route. The evolution of the cell's parameters and the refinement of the crystal structure close to the onset of the reaction identified a topochemical polymerization path, corroborated by reaction kinetics data by infrared spectroscopy and by computed polymer structures, suggesting a complex growth process, resulting in a distinctly different material compared to that formed upon non-hydrostatic compression. These findings underscore the pivotal role of compression conditions in determining the reaction pathways of azobenzene, providing novel insights for its application in nanomaterial synthesis.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775905","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

Electric-Field-Induced Covalent Condensation of Boronic Acids in Water Microdroplets 电场诱导水微滴中硼酸的共价缩合

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-04 DOI: 10.1039/d5sc01466b

Yue-Wen Zhou, Ming-Yang Jia, Jun-Lei Yang, Qinlei Liu, Zhenfeng Cai

引用次数: 0

Manipulating Room-Temperature Phosphorescence by Electron-Phonon Coupling

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-04 DOI: 10.1039/d5sc02149a

Liangwei Ma, Muyu Cong, Siyu Sun, Xiang Ma

引用次数: 0

Rapid synthesis of glycosylated insulins by flow-based peptide synthesis

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-04 DOI: 10.1039/d5sc01670c

Yuta Maki, Surin K. Mong, Chaitra Chandrashekar, Briony E. Forbes, Mohammed Akhter Hossain, Shintaro Yamaguchi, Colin M. Fadzen, Yasuhiro Kajihara, Bradley L. Pentelute

{"title":"Rapid synthesis of glycosylated insulins by flow-based peptide synthesis","authors":"Yuta Maki, Surin K. Mong, Chaitra Chandrashekar, Briony E. Forbes, Mohammed Akhter Hossain, Shintaro Yamaguchi, Colin M. Fadzen, Yasuhiro Kajihara, Bradley L. Pentelute","doi":"10.1039/d5sc01670c","DOIUrl":"https://doi.org/10.1039/d5sc01670c","url":null,"abstract":"Insulin is a key life-saving drug for patients with diabetes and is used clinically worldwide. To address the physicochemical challenges of insulin, such as low solubility and aggregation, glycosylated insulins have been chemically synthesized, exhibiting improved stability due to the hydration effect of glycans. In this work, we demonstrated the rapid synthesis of glycosylated insulins (glycoinsulins) using flow-based solid-phase peptide synthesis (SPPS). The insulin A-chain and glycosylated B-chain were synthesized by flow-based SPPS, with each elongation cycle completed in just 3 minutes. Through our investigations, the glycosylation step was successfully performed within 10 minutes under optimized flow-based conditions. Additionally, we examined the incorporation of dipeptide units (isoacyl dipeptide and pseudoproline) under flow conditions and demonstrated efficient peptide elongation by combining flow-based SPPS with these dipeptide units. The synthesized A- and B-chains were subsequently used for the stepwise formation of disulfide bond linkages. The resulting glycoinsulins exhibited comparable binding affinities to insulin receptors. These findings highlight a novel flow-based approach for the rapid synthesis of glycosylated peptide and protein drugs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"58 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775903","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

Integration of RNAseq transcriptomics and N-glycomics reveal biosynthetic pathways and predict structure-specific N-glycan expression

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-04 DOI: 10.1039/d5sc00467e

Michael Russelle S. Alvarez, Xavier A. Holmes, Armin Oloumi, Sheryl Joyce Grijaldo-Alvarez, Ryan Schindler, Qingwen Zhou, Anirudh Yadlapati, Atit Silsirivanit, Carlito B. Lebrilla

{"title":"Integration of RNAseq transcriptomics and N-glycomics reveal biosynthetic pathways and predict structure-specific N-glycan expression","authors":"Michael Russelle S. Alvarez, Xavier A. Holmes, Armin Oloumi, Sheryl Joyce Grijaldo-Alvarez, Ryan Schindler, Qingwen Zhou, Anirudh Yadlapati, Atit Silsirivanit, Carlito B. Lebrilla","doi":"10.1039/d5sc00467e","DOIUrl":"https://doi.org/10.1039/d5sc00467e","url":null,"abstract":"The processes involved in protein N-glycosylation represent new therapeutic targets for diseases but their stepwise and overlapping biosynthetic processes make it challenging to identify the specific glycogenes involved. In this work, we aimed to elucidate the interactions between glycogene expression and N-glycan abundance by constructing supervised machine-learning models for each N-glycan composition. Regression models were trained to predict N-glycan abundance (response variable) from glycogene expression (predictors) using paired LC-MS/MS N-glycomic and 3′-TagSeq transcriptomic datasets from cells derived from multiple tissue origins and treatment conditions. The datasets include cells from several tissue origins – B cell, brain, colon, lung, muscle, prostate – encompassing nearly 400 N-glycan compounds and over 160 glycogenes filtered from an 18 000-gene transcriptome. Accurate models (validation R2 > 0.8) predicted N-glycan abundance across cell types, including GLC01 (lung cancer), CCD19-Lu (lung fibroblast), and Tib-190 (B cell). Model importance scores ranked glycogene contributions to N-glycan predictions, revealing significant glycogene associations with specific N-glycan types. The predictions were consistent across input cell quantities, unlike LC-MS/MS glycomics which showed inconsistent results. This suggests that the models can reliably predict N-glycosylation even in samples with low cell amounts and by extension, single-cell samples. These findings can provide insights into cellular N-glycosylation machinery, offering potential therapeutic strategies for diseases linked to aberrant glycosylation, such as cancer, and neurodegenerative and autoimmune disorders.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"183 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775901","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

Atomic Surface Structure for Unraveling the Trade-off between the Propane Dehydrogenation Activity and Anti-Deactivation of PtSn Catalysts

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-04 DOI: 10.1039/d5sc01513h

Mingxin Lv, Qiang Li, Fan Xue, Zhiguo Li, Peixi Zhang, Yue Zhu, Longlong Fan, Jianrong Zeng, Qiheng Li, Xin Chen, Kun Lin, Jinxia Deng, Xianran Xing

{"title":"Atomic Surface Structure for Unraveling the Trade-off between the Propane Dehydrogenation Activity and Anti-Deactivation of PtSn Catalysts","authors":"Mingxin Lv, Qiang Li, Fan Xue, Zhiguo Li, Peixi Zhang, Yue Zhu, Longlong Fan, Jianrong Zeng, Qiheng Li, Xin Chen, Kun Lin, Jinxia Deng, Xianran Xing","doi":"10.1039/d5sc01513h","DOIUrl":"https://doi.org/10.1039/d5sc01513h","url":null,"abstract":"In commercial Pt-based propane dehydrogenation catalysts, Sn doping is a fascinating strategy to suppress side reactions and optimizing selectivity. Nevertheless, excessive Sn incorporation results in a decline of surface Pt sites, leading to a significant reduction in catalytic activity. It challenges the precision of surface chemical design and the atomic unraveling of surface coordination are critical to resolving the inherent trade-off between catalytic activity and anti-deactivation. In this work, we modulated PtSn catalyst surface structures by controlling Sn content, achieving optimal activity, anti-deactivation, and selectivity. Building upon the average structural characterization, we have further resolved three-dimensional atomic configurations and extracted surface structures of catalysts by integrating Reverse Monte Carlo method with pair distribution function analysis. It was found that the increasing Sn content enhances anti-deactivation by reducing surface Pt-Pt coordination numbers, this effect reaches saturation when the coordination number on the surface approaches approximately 3. Beyond this critical threshold, additional Sn incorporation compromises activity through Pt site blockage while offering negligible effect on anti-deactivation. These findings provide clear guidelines for the rational surface design of nanocatalysts and synthesis of high-performance platinum-based catalysts with superior catalytic properties.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"37 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775909","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

Base-Stabilized Acyclic Amino(ylidyl)silylenes: Electron-Rich Donors for the Stabilization of Silicon-Element Multiple Bonds

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-03 DOI: 10.1039/d5sc01812a

Felix Krischer, Stephan Mayer, Lennart Hensle, Daniel Knyszek, Heidar Darmandeh, Viktoria H. Gessner

{"title":"Base-Stabilized Acyclic Amino(ylidyl)silylenes: Electron-Rich Donors for the Stabilization of Silicon-Element Multiple Bonds","authors":"Felix Krischer, Stephan Mayer, Lennart Hensle, Daniel Knyszek, Heidar Darmandeh, Viktoria H. Gessner","doi":"10.1039/d5sc01812a","DOIUrl":"https://doi.org/10.1039/d5sc01812a","url":null,"abstract":"Increasing the donor strength of Lewis bases is a viable strategy to stabilize reactive species. Herein, we utilize the strong electron-releasing power of ylide substituents to gain access to electron-rich silylenes. Based on the Roesky’s amidinato chlorosilylene scaffold, we succeeded in isolating two amino(ylidyl)silylenes with a tosyl and cyano group in the ylide backbone, respectively. The tosyl system revealed to be the most electron-rich silylene known to date as measured by its Tolman electronic parameter. DFT studies showed that the ylide acts as a σ and π-donor, transferring electron-density into the empty p-orbital of the silicon center, thus resulting in its electron-richness and stability. The strong donor capacity of the silylene was used to stabilize further reactive silicon species: While treatment with carbon disulfide led to the formation of silylene-CS₂ complexes, the reaction with N₂O or CO₂ was found to depend on the electronic and steric properties of the ylide substituent. Whereas the tosyl system yielded a room-temperature stable silanone, the cyano-substituted silylene formed a carbonate complex with CO₂ and a dimeric silanone with N₂O. Additionally, both silylenes facilitated the isolation of silicon compounds with extended π-conjugated units, highlighting the potential of ylide substituents to stabilize unusual bonding situations.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"62 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767006","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

Mechanically Tunable Porous Gels Constructed via the Dual Co-ordination/Covalent Polymerization of Coumarin-Functionalized Rhodium-Organic Cuboctahedra

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-03 DOI: 10.1039/d5sc00535c

David W. Burke, Masataka Yamashita, Zaoming Wang, Mako Kuzumoto, Kenji Urayama, Kei Saito, Shuhei Furukawa

{"title":"Mechanically Tunable Porous Gels Constructed via the Dual Co-ordination/Covalent Polymerization of Coumarin-Functionalized Rhodium-Organic Cuboctahedra","authors":"David W. Burke, Masataka Yamashita, Zaoming Wang, Mako Kuzumoto, Kenji Urayama, Kei Saito, Shuhei Furukawa","doi":"10.1039/d5sc00535c","DOIUrl":"https://doi.org/10.1039/d5sc00535c","url":null,"abstract":"Polymer-based soft materials constructed from defined molecular pores, such as metal-organic polyhedra (MOPs), promise to merge the outstanding and diverse mechanical properties of conventional nonporous polymers with atomically-precise molecular recognition capabilities. Thus far, soft MOP networks have been constructed primarily using rigid, labile coordination bonds or dynamic covalent bonds, providing static networks without intrinsic mechanisms to optimize their response to mechanical stimuli. Here, we report the construction of flexible, doubly crosslinked MOP gels via mutually compatible coordination and covalent polymerization techniques. Our method employs dirhodium paddlewheel-based MOPs bearing both open metal sites, which enable their coordination-driven assembly, and photodimerizable coumarin side chains for covalent polymerization (Coumarin-RhMOPs). Incubation of Coumarin-RhMOPs with ditopic linkers enabled their coordination-driven polymerization into porous colloidal gels. Site-selective irradiation of coordination-linked Coumarin-RhMOP gels afforded doubly crosslinked gels with improved strain tolerance and higher stiffness. Selective dissociation of coordination-crosslinkers provided highly deformable covalent Coumarin-RhMOP gels. The postsynthetic addition of ditopic ligands to covalent gels enabled the reversible modulation of their mechanical properties. These findings highlight the possibility of incorporating multiple responsive crosslinks in porous MOP networks to rationally tune their responses to mechanical stress, paving the way to their practical implementation as next-generation chemical separators, catalysts, and drug delivery vehicles.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"80 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775910","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

Quantification of the effects of n-π* interactions on the H-bonding properties of amide groups

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-03 DOI: 10.1039/d4sc08331h

Fergal E. Hanna, Andrew D. Bond, Christopher A. Hunter

{"title":"Quantification of the effects of n-π* interactions on the H-bonding properties of amide groups","authors":"Fergal E. Hanna, Andrew D. Bond, Christopher A. Hunter","doi":"10.1039/d4sc08331h","DOIUrl":"https://doi.org/10.1039/d4sc08331h","url":null,"abstract":"The n-π* interaction is postulated to play a key role in the folding of proteins, especially in proline-rich structures such as collagen, and cooperativity between H-bonding and the n-π* interaction has been proposed. In order to obtain experimental evidence for these cooperative effects, the H-bond acceptor properties of secondary amides with and without the capacity to form an intramolecular n-π* interaction were measured. UV-vis absorption and 13C NMR titrations were used to investigate the intermolecular H-bonded complexes formed with 2-methyl-4-nitro-phenol and perfluoro-tert-butanol, and hence quantify the H-bond acceptor properties of the amide carbonyl oxygens. For an N-acylproline derivative, the presence of an intramolecular n-π* interaction between two amide groups was confirmed by X-ray crystallography, but the solution titrations show that associated changes in the H-bond acceptor strength of the amide carbonyl oxygen group are negligible. The free energy contribution due to cooperativity between the intramolecular n-π* interaction and the intermolecular H-bond was found to be within the error of the experiment (<1 kJ mol−1). The results suggest that any contributions to the thermodynamic stability of folded proteins due to such cooperativity are small.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"37 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767008","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