Structural Chemistry最新文献

{"title":"J. Fraser Stoddart (1942–2024) Nobel laureate for molecular machines—author in Structural Chemistry","authors":"Istvan Hargittai","doi":"10.1007/s11224-025-02481-y","DOIUrl":"10.1007/s11224-025-02481-y","url":null,"abstract":"<div><p>In a 1999 article of <i>Structural Chemistry</i>, the recently deceased J. Fraser Stoddart and two associates surveyed the interplay between the synthesis of functioning supramolecular systems and their X-ray crystallographic investigation. Furthermore, they charted the anticipated development and necessary work for creating “intelligent” materials with predetermined functions. This was part of Stoddart’s discoveries in creating molecular machines that brought him a share of the chemistry Nobel Prize in 2016.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 3","pages":"1135 - 1137"},"PeriodicalIF":2.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143904846","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Forty years of the discovery of buckminsterfullerene","authors":"Istvan Hargittai","doi":"10.1007/s11224-025-02471-0","DOIUrl":"10.1007/s11224-025-02471-0","url":null,"abstract":"<div><p>The discovery of buckminsterfullerene 40 years ago was a major event in chemistry and materials science. It was also a discovery outside the “box” as Harold W. Kroto, Richard E. Smalley, Robert F. Curl, and their students assigned a structure to the species appearing as a prominent peak in the mass spectrum. Earlier, Eiji Osawa and Elena G. Galpern had suggested its existence and truncated icosahedral shape. This field of science began unprecedented progress when Donald R. Huffman, Wolfgang Krätschmer, and their associates produced the actual material.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 3","pages":"779 - 782"},"PeriodicalIF":2.1,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143904749","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Consecutive Friedel–Crafts acyl rearrangements and Scholl reactions of dinaphthyl ketones","authors":"Yaacov Netanel Oded,&nbsp;Tahani Mala’bi,&nbsp;Sergey Pogodin,&nbsp;Shmuel Cohen,&nbsp;Benny Bogoslavsky,&nbsp;P. Ulrich Biedermann,&nbsp;Israel Agranat","doi":"10.1007/s11224-024-02445-8","DOIUrl":"10.1007/s11224-024-02445-8","url":null,"abstract":"<div><p>The three dinaphthylketone constitutional isomers, <b>1,1′-NA</b>_<b>2</b><b>CO</b>, <b>1,2′-NA</b>_<b>2</b><b>CO</b>, and <b>2,2′-NA</b>_<b>2</b><b>CO</b>, have been subjected to Friedel–Crafts Acylation (polyphosphoric acid (PPA), 90–300°C, 12 h) and Scholl reaction (AlCl₃/NaCl, 120–300°C, 4 h). The resulting product mixtures are analyzed by NMR and separated by column chromatography. The starting ketones and the products have been calculated with DFT, B3LYP/6-311G**, to support analysis of the reaction mechanisms. The three dinaphthyl ketones have three, four, and three <i>E,Z</i>-conformations, which may potentially give ten Scholl reaction products by <i>ortho-ortho</i>, <i>ortho-peri</i>, and <i>peri-peri</i> couplings. In PPA, the products formed at relatively low temperatures are due to Scholl reactions of the starting ketones. At higher temperatures, naphthalene is formed and Friedel Crafts acyl rearrangements (FCAcRs) <b>1,1′-NA</b>_<b>2</b><b>CO</b> → <b>1,2′-NA</b>_<b>2</b><b>CO</b> → <b>2,2′-NA</b>_<b>2</b><b>CO</b> are observed. At high temperatures, additional Scholl products show that complex multi-step reactions occur including FCAcRs in both directions and cyclic FCAcRs of Scholl products. The reactions in AlCl₃/NaCl are highly selective, giving only the 6-ring Scholl cyclization products 13<i>H</i>-dibenzo[<i>a,i</i>]fluoren-13-one and 7<i>H</i>-benzo[<i>hi</i>]chrysen-7-one (<b>B</b><b><i>hi</i></b><b>CO</b>) and 7<i>H</i>-benzo[<i>de</i>]naphthacen-7-one (<b>B</b><b><i>de</i></b><b>NCO</b>). Up to 240°C <b>1,1′-NA</b>_<b>2</b><b>CO</b> forms <b>B</b><b><i>hi</i></b><b>CO</b> and up to 220°C <b>1,2′-NA</b>_<b>2</b><b>CO</b> forms <b>B</b><b><i>de</i></b><b>NCO</b>. At higher temperatures, both polycyclic aromatic ketones are formed from each of the three dinaphthyl ketones indicating FCAcRs. The detailed analysis of the experimental data in combination with the DFT calculations shows that FCAcRs are reactions in both directions in PPA and AlCl₃/NaCl, substantiating Gore’s 1955 proposition that <i>the Friedel–Crafts acylation reaction of reactive aromatic hydrocarbons is a reversible process</i>. The lower onset temperatures and selectivity of cyclization products suggest lower activation energies for Scholl reactions as compared to FCAcRs in PPA and even more pronounced in AlCl₃/NaCl. The common network of reaction pathways underlying the reactions in both media highlights the linkage between Friedel–Crafts acyl rearrangements and Scholl reactions.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 2","pages":"401 - 432"},"PeriodicalIF":2.1,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11224-024-02445-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143621774","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nobel Prize for the discovery of microRNA and its role in gene regulation","authors":"Krisztina Hagymási","doi":"10.1007/s11224-025-02462-1","DOIUrl":"10.1007/s11224-025-02462-1","url":null,"abstract":"<div><p>The Nobel Prize 2024 in Physiology or Medicine has been awarded for the discovery of miRNA and its role in post-transcriptional gene regulation. Firstly, the results were thought to be irrelevant to humans, but nowadays, at least 30% of the known miRNAs could be used as novel biomarkers for screening human diseases and therapeutic purposes targeting manipulation of cell functions under examinations.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 2","pages":"759 - 765"},"PeriodicalIF":2.1,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622176","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Correction to: Determination of dissociation constants of cephalosporin antibiotics by cellmetry method","authors":"Malek Sadatsharifi,&nbsp;Mihály Purgel","doi":"10.1007/s11224-025-02451-4","DOIUrl":"10.1007/s11224-025-02451-4","url":null,"abstract":"","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 2","pages":"757 - 758"},"PeriodicalIF":2.1,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11224-025-02451-4.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622102","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Towards the computational design of organic molecules with specified properties","authors":"Anton B. Zakharov,&nbsp;Mariia Kyrpa,&nbsp;Alexander V. Kyrychenko,&nbsp;Sergiy M. Kovalenko,&nbsp;Oleg N. Kalugin,&nbsp;Volodymyr V. Ivanov,&nbsp;Ludwik Adamowicz","doi":"10.1007/s11224-024-02441-y","DOIUrl":"10.1007/s11224-024-02441-y","url":null,"abstract":"<div><p>In this work, we present and test a procedure for generating a chemical virtual library and its subsequent use to select molecular systems with desired properties. The library consists of molecular structures generated from a set of chemical fragments. As an example, we consider two tasks. The first one involves identifying structures with specific spectral properties, particularly concerning the UV–Vis region of the spectrum. To address this, the thiophene cycles with typical donor (dimethylamino) and acceptor (nitro) substituents are chosen as the molecular building blocks. First, the molecules from the derived virtual library are subject to computational screening using the semi-empirical tight binding density-functional method. The primary objective of the screening is to identify molecular structures that exhibit desired spectral properties, especially absorption in the long-wavelength region. Second, for the most promising structures identified in the initial screening, more accurate TD-DFT (B3LYP/cc-pVDZ) calculations are performed. Additionally, the advantage of the developed approach for library generation, aimed at further investigation of biological activity, is illustrated using an example involving papain-like protease (PLpro) inhibitors of the SARS-CoV-2 virus. The calculation scheme used in the considered examples is implemented in the Python program suite QUASAR.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 2","pages":"723 - 738"},"PeriodicalIF":2.1,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622276","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A combinatorial exploration of a very large set of azaboles","authors":"Ibon Alkorta,&nbsp;Maxime Ferrer,&nbsp;Goar Sánchez-Sanz,&nbsp;Felipe Reviriego,&nbsp;José Elguero","doi":"10.1007/s11224-024-02422-1","DOIUrl":"10.1007/s11224-024-02422-1","url":null,"abstract":"<div><p>The thermodynamic properties of 778 azaboles, including the known pyrazaboles, imidazaboles, and triazaboles, have been theoretically calculated at the CBS-QB3 level. Pólya enumeration theorem was used to determine the number of skeletons of azaboles (237 neutral systems), followed by an exploration and generation of the whole space of N–H tautomers. The experimental X-ray geometries, B–C and B–N distances and folding angles, were compared with those of the calculated geometries. Using Free-Wilson (or absence-presence) matrices and multiple regression analysis, the fragments’ contribution to different enthalpies was calculated. Finally, a machine learning model based on Gaussian Process Regression has been created to predict the Δ<i>H</i>°_f of the azaboles together with their structural characteristics.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 3","pages":"1115 - 1133"},"PeriodicalIF":2.1,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143904870","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Different topology of mixed valence CoIICoIII complexes with SCN anions and hydrazone–pyridine-based ligands","authors":"Ghodrat Mahmoudi,&nbsp;Alexander S. Novikov,&nbsp;Tomislav Balić,&nbsp;Ennio Zangrando,&nbsp;Jonathan M. White,&nbsp;Bagher Eftekhari-Sis","doi":"10.1007/s11224-024-02442-x","DOIUrl":"10.1007/s11224-024-02442-x","url":null,"abstract":"<div><p>Two novel mixed valence Co^IICo^III complexes [Co₄^II(SCN)₁₂(EtOH)₂Co₄^III(L1)₈] (<b>1</b>) and [Co^II(SCN)₂Co₂^III(L2)₄]_<i>n</i> (<b>2</b>) (HL1 = <i>N’</i>-(1-(pyridin-2-yl)ethylidene)nicotinohydrazide and HL2 = <i>N’</i>-(phenyl(pyridin-2-yl)methylene)isonicotinohydrazide) have been synthesized and structurally characterized by the single crystal X-ray crystallography. In both cases, the deprotonated ligands HL1 and HL2 behave as chelating species toward Co^III, further connecting Co^II fragments through the nicotine pyridine donors. A different topology is observed in the solid state of these complexes, complex <b>1</b> being an octanuclear cyclic species, while <b>2</b> is a 1D coordination polymer. The DFT calculations followed by the topological analysis of the electron density distribution have shown the existence of interesting non-covalent S···<i>π</i>-system interactions in <b>1</b>. The CSD database search for similar supramolecular motif involving NCS anion has shown that the number and strength of S···<i>π</i> interactions depend both on acidity of metal cation and number aromatic systems in the molecular structure of ligand.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 3","pages":"1105 - 1113"},"PeriodicalIF":2.1,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143904830","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis, spectroscopic and structural characterization of cyclometallated rhodium(III) complexes with 1-phenyl-1H-pyrazole and α-diimines ligands, comparison with their iridium(III) analogues","authors":"Anna Kamecka,&nbsp;Andrzej Kapturkiewicz,&nbsp;Patryk Wójcik,&nbsp;Kinga Suwińska,&nbsp;Joanna Masternak,&nbsp;Natalia Barbarczyk","doi":"10.1007/s11224-024-02439-6","DOIUrl":"10.1007/s11224-024-02439-6","url":null,"abstract":"<div><p>The paper deals with the synthesis of a series of cationic [Rh(ppz)₂(N^N)]⁺ complexes containing deprotonated 1-phenyl-1<i>H</i>-pyrazole as cyclometallating (C^N) ligands and α-diimines (2,2’-bipyridine, 1,10-phenanthroline and its derivatives) as ancillary (N^N) ligands in the form of salts with PF₆ ⁻ counter ions. These complexes were obtained from [(ppz)₂Rh-<i>μ</i>-Cl]₂ precursor through cleaving the <i>μ</i>-dichloro-bridged dimer with N^N ancillary ligands. The complexes were identified by means of NMR spectroscopy and MS spectrometry and their molecular structures were finally confirmed by X-ray crystallography. These complexes showed strong luminescence in MeOH/EtOH 1:1 glasses at 77 K but were very week or almost non-emitting species in MeCN solutions at room temperature. Their emission properties were compared to analogues Ir(III) complexes.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 2","pages":"709 - 722"},"PeriodicalIF":2.1,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143621947","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Geometrical and thermodynamical stability of the adducts of the phytochemicals of Swertia chirayita (Roxb. Ex Fleming) with a protein of Plasmodium falciparum","authors":"Ram Lal Swagat Shrestha,&nbsp;Bishnu Prasad Marasini,&nbsp;Jhashanath Adhikari Subin","doi":"10.1007/s11224-024-02415-0","DOIUrl":"10.1007/s11224-024-02415-0","url":null,"abstract":"<div><p>The global economic burden of malaria is rising due to climate change, and the search for effective and specific drugs against it that are affordable has become essential. The phytochemicals with ethnobotanical values are relatively safer and are a viable option for their use as therapeutics. The chemical components of a plant, <i>Swertia chirayita</i> (Roxb. Ex Fleming), showed strong binding potential against the parasite membrane protein of <i>Plasmodium falciparum</i> (PDB ID: 5K8S), a causative agent of the disease, as determined from computational methods. The docking scores of the top two candidates, amarogentin and swertinin, were determined to be − 10.064 kcal/mol and − 9.904 kcal/mol, respectively, with the native ligand possessing a higher value of − 8.395 kcal/mol. The protein–ligand complexes formed by these top two ligands were geometrically and thermodynamically stable, as revealed by several parameters extracted from the molecular dynamics simulations. Especially, the smooth nature of ligand RMSD curves denoted the attainment of equilibrium and binding free energy changes; Δ<i>G</i>_BFE &lt; 0 predicted the sustained thermodynamical spontaneity of the complex formation reaction. The preliminary results suggest that the hit phytochemicals could inhibit the normal functioning of the target protein and are recommended for further experimental trials. The traditional knowledge of the plants with therapeutic values could be extended to modern medicines with molecular-level understanding and be used in the drug design process in a low-resource setting.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 3","pages":"1091 - 1104"},"PeriodicalIF":2.1,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143904823","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}