{"title":"Economically Scalable Cu-based MOFs: Vital Role of Structural Integrity towards Selectivity on Azeotropic Ethanol Dehydration.","authors":"Yollada Inchongkol, Kanyaporn Adpakpang, Panyapat Ponchai, Thassanant Atithep, Nattamon Chitterisin, Somlak Ittisanronnachai, Teera Butburee, Sareeya Bureekaew","doi":"10.1002/chem.202402509","DOIUrl":"10.1002/chem.202402509","url":null,"abstract":"<p><p>A facile, green, and economical method for the scalable synthesis of hydrophilic copper-triazole metal-organic frameworks (Cu-trz) is demonstrated. Numerous open metal sites within the highly crystalline porous structure of Cu-trz are generated through mild thermal activation, enabling its application in liquid-phase ethanol dehydration under ambient conditions. The frameworks with distinct crystallinity and particle sizes were achieved by modifying the synthesis process. The high crystallinity of the framework plays an exclusive role in enhancing water adsorption capacity. With selective water adsorption comparable to commercial zeolite 3 A, Cu-trz MOF emerges as a promising candidate for cost-effective water-ethanol separation.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202402509"},"PeriodicalIF":3.9,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142764856","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":"Fluorine Labeling and <sup>19</sup>F NMR Spectroscopy to Study Biological Molecules and Molecular Complexes.","authors":"Yannick Werle, Michael Kovermann","doi":"10.1002/chem.202402820","DOIUrl":"10.1002/chem.202402820","url":null,"abstract":"<p><p>High-resolution nuclear magnetic resonance (NMR) spectroscopy represents a key methodology for studying biomolecules and their interplay with other molecules. Recent developments in labeling strategies have made it possible to incorporate fluorine into proteins and peptides reliably, with manageable efforts and, importantly, in a highly site-specific manner. Paired with its excellent NMR spectroscopic properties and absence in most biological systems, fluorine has enabled scientists to investigate a rather wide range of scientific objectives, including protein folding, protein dynamics and drug discovery. Furthermore, NMR spectroscopic experiments can be conducted in complex environments, such as cell lysate or directly inside living cells. This review presents selected studies demonstrating how <sup>19</sup>F NMR spectroscopic approaches enable to contribute to the understanding of biomolecular processes. Thereby the focus has been set to labeling strategies available and specific NMR experiments performed to answer the underlying scientific objective.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202402820"},"PeriodicalIF":3.9,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142520492","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":"Active Photonic Glass for Hydrogen Generation.","authors":"Cong Wang, Masa Johar, Wahid Ullah, Erwan Paineau, Jingwei Li, Mohamed Nawfal Ghazzal","doi":"10.1002/chem.202402141","DOIUrl":"10.1002/chem.202402141","url":null,"abstract":"<p><p>Chirality is vital in many living species since it is responsible for structural iridescent coloration and plays a key role in light harvesting during natural photosynthesis. Developing photoactive materials with such chiral structures is a challenging but promising strategy for energy applications. Here, we present a straightforward method to establish an active photonic glass obtained through the co-condensation of tetramethyl orthosilicate (TMOS) and titanium diisopropoxide bis(acetylacetonate) (TAA) dissolved in a liquid crystal formed from cellulose nanocrystalline (CNC). The inorganic glass maintains a long range of chiral nematic ordering, displaying iridescent colors characterized by a Bragg peak reflection. The reflected wavelengths are tuned all over the UV-visible range, demonstrating that the replica of the chiral nematic structure generates photonic properties. Incorporation of gold nanoparticles (Au NPs) into the films is further performed by impregnation/chemical reduction. We show that the charge carrier density and photocatalytic H<sub>2</sub> generation were amplified when the photonic band gap edges matched the absorbance of the TiO<sub>2</sub> and localized surface plasmon resonance (LSPR) of AuNPs. This photocatalytic glass with chiral nematic ordering and a tunable photonic bandgap paves the way for the development of metamaterials with new applications, such as asymmetric photocatalysis.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202402141"},"PeriodicalIF":3.9,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11724248/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574928","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sven Mörsel, Christian L Ritterhoff, René Kellner, Bernd Meyer, Andreas Hirsch
{"title":"N-Heterocycle-Substituted Hexa-peri-Hexabenzocoronenes with Windmill Architectures.","authors":"Sven Mörsel, Christian L Ritterhoff, René Kellner, Bernd Meyer, Andreas Hirsch","doi":"10.1002/chem.202403124","DOIUrl":"10.1002/chem.202403124","url":null,"abstract":"<p><p>We describe the synthesis and computational investigation of N-heterocycle-substituted hexa-peri-hexabenzocoronenes (HBCs). Following our method for the preparation of thioether-substituted HBCs, we prepared pyrrole-, indole-, carbazole-, and 1H-benz[g]indole-substituted HBCs from the corresponding fluorinated precursors under microwave irradiation. A series of polysubstituted benzoindole-HBCs with windmill architectures was also synthesized using the polyfluorinated HBC analogs, and the substituent effects on the electronic properties of the HBC core were investigated. Similar to the thioether substituted HBCs, the nature of the heterocycle does not influence the optoelectronic properties of the HBC core. The attachment of multiple benzoindole substituents leads to a bathochromic shift of the absorption and emission spectra, comparable to our previous studies. Due to the circular arrangement of the benzoindole moiety, the attachment of multiple substituents results in the presence of multiple conformers at room temperature. The rotation barrier can be overcome by heating the compounds to 323-333 K. Additionally, the investigation of the relaxed geometries shows two π-stacking motifs within the conformers.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403124"},"PeriodicalIF":3.9,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542336","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}
Daiana Cabrosi, Juan H Mecchia Ortiz, Carlos Cruz, Verónica Paredes-García, Pablo Alborés
{"title":"A {Cr<sub>4</sub>Ln<sub>2</sub>} Complex with Exchange Coupled {Cr<sub>2</sub>} Units: Structural Description and Magnetic Study.","authors":"Daiana Cabrosi, Juan H Mecchia Ortiz, Carlos Cruz, Verónica Paredes-García, Pablo Alborés","doi":"10.1002/chem.202403118","DOIUrl":"10.1002/chem.202403118","url":null,"abstract":"<p><p>We have prepared and structurally characterized pivalate based {Cr<sup>III</sup> <sub>4</sub>Ln<sup>III</sup> <sub>2</sub>} complexes with Ln = Dy and Gd as well as the Y analogue, with the overall formula [Cr<sup>III</sup> <sub>4</sub>Ln<sup>III</sup> <sub>2</sub>(mdea)<sub>2</sub>(piv)<sub>10</sub>(OH)<sub>4</sub>], Ln = Gd, Dy and Y. We are reporting a detailed experimental magnetic properties study, including magnetization relaxation dynamics and calorimetric data, supported with quantum chemical calculations. The synthesis of the Y derivative, allowed to precisely identify the Cr(III)-Cr(III) exchange interaction magnitude which proved moderately strong and in agreement with known magneto-structural correlations. This result agrees with the observed double bridged {Cr<sub>2</sub>-μOH-μOR} units within the {Cr<sub>4</sub>Ln<sub>2</sub>} complexes. The Gd(III) complex magnetic properties can be properly described with the already established exchange coupled {Cr<sub>2</sub>} units, and a unique Gd(III)-Cr(III) exchange coupling parameter which proved anti-ferromagnetic in nature. The MCE characterization of this complex based on magnetization and calorimetric data down to 2 K affords a moderate entropy change value, mainly affected by the strong Cr-Cr exchange interaction. The complex with Ln = Dy, showed SMM behaviour below 10 K under 0 DC applied field with negligible field dependence up to 3000 Oe and 10 kHz of AC field frequency. Two relaxation processes are clearly distinguished, with thermal barriers for an Orbach mechanism of ca. 20 cm<sup>-1</sup> and 40 cm<sup>-1</sup>.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403118"},"PeriodicalIF":3.9,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142764790","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":"Solvent-Dependent C(sp3)-CF3 Reductive Elimination from Neutral Four-Coordinate Cu(III) Complexes.","authors":"Yuecheng Weng, Deng Pan, Jian Wu, Xuebing Leng, Xiao-Song Xue, Qilong Shen","doi":"10.1002/chem.202403620","DOIUrl":"https://doi.org/10.1002/chem.202403620","url":null,"abstract":"<p><p>A solvent dependent C(sp3)-CF3 bond-forming reductive elimination from neutral four-coordinate Cu(III) complexes [(L)Cu(CF3)2(CH2CO2tBu)] (L = pyridine or its derivatives) is described. Reactions in less polar solvent ClCH2CH2Cl proceed via a concerted bond breaking/bond forming process along with the reorientation of the ligand, while reaction in polar solvent DMF occurs via a rate limiting ligand-dissociation, followed by C(sp3)-CF3 reductive elimination from the resulting three-coordinate intermediate. These mechanistic proposals are supported by kinetic studies that included ligand and temperature effects, as well as DFT calculations.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403620"},"PeriodicalIF":3.9,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142941854","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}
Chivukula Sastri, Payal Panwar, Shreya Rawat, Rolly Yadav, Sam de Visser, Jason Z He, Henrik P H Wong
{"title":"Influence of Asymmetrical Ligand Substitution on the Formation, Stability, and Reactivity of Ruthenium(III)-Hypochlorite Complexes.","authors":"Chivukula Sastri, Payal Panwar, Shreya Rawat, Rolly Yadav, Sam de Visser, Jason Z He, Henrik P H Wong","doi":"10.1002/chem.202403892","DOIUrl":"https://doi.org/10.1002/chem.202403892","url":null,"abstract":"<p><p>Hypohalites are commonly generated in biological systems, mostly with functions related to defense and immune system response. These hypohalites can bind to metal centers and are known for their strong oxidizing properties that play crucial roles in various biological processes. Herein, we report the synthesis, characterization and reactivity of novel biomimetic Ru(III)-hypochlorite complexes and focus the work on the electronic effects associated with the incorporation of methyl groups in a pentadentate ligand framework in an asymmetric fashion. The intermediates are stable at room temperature and were characterized by mass spectrometry, UV-vis absorption, resonance Raman and EPR spectroscopy. We show for the first time that the resultant ruthenium-hypochlorite adducts function as an electrophilic oxidant and efficiently catalyze hydrogen atom abstraction reactions from phenol and oxygen atom transfer reactions with dimethylsulfide.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403892"},"PeriodicalIF":3.9,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142941832","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}
Fabian Jester, Tobias Kaczun, Steffen Maier, Paul Meiners, Svenja Weigold, Frank Rominger, Andreas Dreuw, Jan Freudenberg, Uwe H F Bunz
{"title":"Diels-Alder Reactivity of Triisopropylsilyl Ethynyl Substituted Acenes.","authors":"Fabian Jester, Tobias Kaczun, Steffen Maier, Paul Meiners, Svenja Weigold, Frank Rominger, Andreas Dreuw, Jan Freudenberg, Uwe H F Bunz","doi":"10.1002/chem.202403522","DOIUrl":"10.1002/chem.202403522","url":null,"abstract":"<p><p>We investigated the Diels-Alder reaction of 6,13-bis(triisopropylsilylethynyl)pentacene (1) with small dienophiles such as (bridged) dihydronaphthalenes/cyclohexenes that yielded adducts at the central ring, the other dienophiles predominantly or exclusively attacked the unsubstituted off-center ring. The difference in regioselectivity was investigated by DFT calculations. Apart from dispersion interactions, it is due to the steric demand of the dienophiles, which need to fit in between the silylethynyl substituents to react at the central ring. Epoxynaphthalene adducts of 1 as well as its anthracene and tetracene congeners were deoxygenated, easily furnishing triarenobarrelenes with TIPS-ethynyl substituents at the bridgeheads, attractive building blocks for porous solids and higher acene-based trimers.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403522"},"PeriodicalIF":3.9,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142454039","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}
Prasad M Sonawane, Neha Jain, JunHyuk Kim, Su Jeong Park, Sandip V Mulay, Satish Balasaheb Nimse, David G Churchill
{"title":"A Novel Methacryloyl-Masked NIR Fluorescent Probe for Detection of Cysteine and Its Application in Bioimaging.","authors":"Prasad M Sonawane, Neha Jain, JunHyuk Kim, Su Jeong Park, Sandip V Mulay, Satish Balasaheb Nimse, David G Churchill","doi":"10.1002/chem.202402840","DOIUrl":"10.1002/chem.202402840","url":null,"abstract":"<p><p>Cysteine (Cys) detection is recognized as an essential element in this investigation due to the critical function of Cys in several physiological processes in living organisms. A new NIR fluorescent probe SNC-Cys has been synthesized by incorporating a five-membered malononitrile derivatized ring as an electron withdrawing group, and a methacryloyl group detection moiety for cysteine. After adding Cys, SNC-Cys shows an emission of 654 nm and further works as a \"Turn-on\" probe via ICT photomechanism. SNC-Cys has high sensitivity and selectivity for Cys (LOD=0.46 μM) and can discriminate it from other closely related amino acids, molecules with structural similarity, and in some cases very close functional group likeness. Thus, these results allow the effective imaging of Cys in living A549 cells which indicates good cell permeability and high applicability in live cell imaging. This study anticipates that SNC-Cys could be an aid in the detection of Cys-relevant diseases.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202402840"},"PeriodicalIF":3.9,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142674640","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":"Design Concepts of High-Entropy Materials for Zinc Ion Batteries.","authors":"Kaisheng Sun, Jiaru Li, Liang Li, Danming Chao","doi":"10.1002/chem.202402859","DOIUrl":"10.1002/chem.202402859","url":null,"abstract":"<p><p>Zinc-ion batteries have emerged as strong candidates for replacing Li/Na-ion batteries owing to their high safety and environmental friendliness. However, the large electrostatic repulsion between the cathode and Zn<sup>2+</sup>, the irreversible growth of zinc dendrites at the anode, and the hydrogen precipitation side reaction in the aqueous electrolyte have hindered the practical application of zinc ion batteries. Fortunately, the emergence of the revolutionary concept of high entropy has provided new opportunities for the development of battery materials. High-entropy materials, with their unique atomic structures and uniform distribution of multiple elements, offer flexible options for material compositions and electronic structures, thus attracting significant attention in battery systems. In this concept article, we summarize the definitions and intrinsic structural characteristics of high-entropy materials and provide a detailed overview of the latest design concepts from the perspectives of cathodes, anodes, and electrolytes. Finally, we outline the challenges faced by high-entropy materials and potential solutions to guide researchers in developing efficient and stable zinc-ion batteries.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202402859"},"PeriodicalIF":3.9,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142724412","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}