ChiralityPub Date : 2024-09-15DOI: 10.1002/chir.23715
Maria Aurora Guarducci, Simone Manetto, Marco Pierini, Giulia Mazzoccanti, Claudio Villani
{"title":"Design, Synthesis, and Applications of Bis-Amido HPLC Pirkle-Type Chiral Stationary Phases","authors":"Maria Aurora Guarducci, Simone Manetto, Marco Pierini, Giulia Mazzoccanti, Claudio Villani","doi":"10.1002/chir.23715","DOIUrl":"https://doi.org/10.1002/chir.23715","url":null,"abstract":"<p>Two different types of chiral stationary phases, based on Pirkle's design, were created by attaching chiral selectors to 3-mercapto silica gel. To prepare the enantiomeric selectors, 3,5-dinitrobenzoyl and naphthyl groups were sequentially added to a chiral 1,2-diaminocyclohexane core. The chiral selectors demonstrated enantioselectivity towards ibuprofen enantiomers in solution, as confirmed by <sup>1</sup>H NMR spectroscopy, and in initial HPLC testing, the enantiomeric selectors showed enantioselectivity for selected racemic solutes (viz., α = 1.27 for1,1′-bi-(2-naphthol)). Molecular docking studies revealed that the chiral selectors had a bent structure and a cleft-like cavity where the analyte could be held during complexation while establishing H-bonding and π–π stacking interactions.</p>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 9","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chir.23715","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142234786","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}
ChiralityPub Date : 2024-09-12DOI: 10.1002/chir.23711
Ummu Ozgun, Hayriye Nevin Genc
{"title":"Catalytic Performance of Chiral Tetraaza-Bridged Calix[4]arene[2]triazine Derivatives for Enantioselective Michael Reactions","authors":"Ummu Ozgun, Hayriye Nevin Genc","doi":"10.1002/chir.23711","DOIUrl":"https://doi.org/10.1002/chir.23711","url":null,"abstract":"<div>\u0000 \u0000 <p>Novel chiral tetraaza-bridged calix[4]arene[2]triazine-based organocatalysts were synthesized and used for catalytic asymmetric Michael reaction of acetylacetone to various aromatic nitrostyrenes. Chiral subunits (<i>R</i>)- and (<i>S</i>)-1,2,3,4-tetrahydro-1-naphthylamine were attached to the tetraaza-bridged calix[4]arene[2]triazine platform in both enantiomeric forms. The <i>R</i> configuration of the major enantiomer of the Michael product was obtained when <b>3a</b> was used as catalyst, and the <i>S</i> configuration was obtained when <b>3b</b> was used as catalyst. This indicated that the configuration of the Michael product was controlled by the chiral calixarene moiety. The Michael adducts were obtained in excellent yields (91%) and enantioselectivities (98%).</p>\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 9","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142231070","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}
ChiralityPub Date : 2024-09-12DOI: 10.1002/chir.23717
Eduard Belonogov, Ekaterina Ermolaeva, Ilya Zinoviev, Zhi-hui Zhang, Vladimir Guskov
{"title":"Enantiomer Recognition by the Difference in Adsorption Rates on the Surfaces of Chiral Crystals","authors":"Eduard Belonogov, Ekaterina Ermolaeva, Ilya Zinoviev, Zhi-hui Zhang, Vladimir Guskov","doi":"10.1002/chir.23717","DOIUrl":"https://doi.org/10.1002/chir.23717","url":null,"abstract":"<div>\u0000 \u0000 <p>The chirality of biopolymers remains one of the mysteries of Life. For such objects, the phenomenon of supramolecular chirality (SMC) is vital. Enantiomers can be recognized by the adsorption on surfaces with SMC. However, the mechanisms of such chiral recognition are still unknown. In this work, the adsorption kinetics of menthol test enantiomers on the surfaces of γ-glycine and NiSO<sub>4</sub>•6H<sub>2</sub>O chiral crystals was studied. It was found that the difference in adsorption was observed in nonequilibrium state more often than in equilibrium. If the enantioselectivity in equilibrium state was observed, the enantioselectivity coefficient α at nonequilibrium conditions was higher. The maximum α in nonequilibrium state was 2.44 for γ-glycine crystals and 2.12 for NiSO<sub>4</sub>•6H<sub>2</sub>O crystals. Even if no differences in adsorption were observed under adsorption–desorption equilibrium conditions, a significant enantioselectivity at nonequilibrium conditions was found. This has proved the possibility of chiral recognition on surfaces with SMC by the differences in adsorption rates. Such novel chiral recognition mechanism can provide enhanced enantioselectivity in adsorption, catalysis, chromatographic separation, and chemical sensing.</p>\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 9","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142174230","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}
ChiralityPub Date : 2024-09-08DOI: 10.1002/chir.23714
{"title":"Correction to “Structural Investigations of Cargo Molecules Inside Icosahedrally Symmetric Encapsulin by VUVCD Spectroscopic Measurements”","authors":"","doi":"10.1002/chir.23714","DOIUrl":"https://doi.org/10.1002/chir.23714","url":null,"abstract":"<p>\u0000 <span>Kumamoto, S</span>, <span>Yamamoto, A</span>, <span>Shiratsuchi, Y</span>, <span>Matsuo, K</span>, <span>Higashiura, A</span>, <span>Hira, D</span>. <span>Structural Investigations of Cargo Molecules Inside Icosahedrally Symmetric Encapsulin by VUVCD Spectroscopic Measurements</span>. <i>Chirality</i>. <span>2024</span>; <span>36</span>(<span>8</span>):e23700, https://doi.org/10.1002/chir.23700.\u0000 </p><p>This article was published ahead of its designation as a themed special issue article and was intended to contain a note saying that it will be published as part of the special issue for “Proceedings of 19th International Conference on Chiroptical Spectroscopy, Hiroshima, Japan 2023.”</p><p>We apologize for this error.</p>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 9","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chir.23714","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142158569","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}
ChiralityPub Date : 2024-08-28DOI: 10.1002/chir.23713
Siva Rama Kasibabu Velugula, Veera Babu Kagita, Ramadas Chavakula, Paul Douglas Sanasi
{"title":"Improved, Efficient, and Simple Methodology for the Resolution of Racemic Benoxaprofen: A Nonsteroidal Anti-Inflammatory Drug (NSAID)","authors":"Siva Rama Kasibabu Velugula, Veera Babu Kagita, Ramadas Chavakula, Paul Douglas Sanasi","doi":"10.1002/chir.23713","DOIUrl":"https://doi.org/10.1002/chir.23713","url":null,"abstract":"<div>\u0000 \u0000 <p>The present article discloses an improved, efficient, and simple resolution methodology for the preparation of (<i>S</i>)-benoxaprofen which is a nonsteroidal anti-inflammatory drug (NSAID). The resolution of racemic benoxaprofen uses an easily available, efficient, recoverable, and cost-effective chiral reagent, namely, (1<i>R</i>,2<i>S</i>)-(+)-<i>cis</i>-1-amino-2-indanol. This novel resolution process is having a very high purity of (<i>S</i>)-benoxaprofen, greater than 99%, substantially free from (<i>R</i>)-benoxaprofen (less than 1%).</p>\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 9","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142100100","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}
ChiralityPub Date : 2024-08-28DOI: 10.1002/chir.23712
Ekaterina V. Semenova, Ekaterina V. Belova, Alexey V. Sulimov, Vladimir B. Sulimov
{"title":"Molecular Docking of Chiral Drug Enantiomers With Different Bioactivities","authors":"Ekaterina V. Semenova, Ekaterina V. Belova, Alexey V. Sulimov, Vladimir B. Sulimov","doi":"10.1002/chir.23712","DOIUrl":"https://doi.org/10.1002/chir.23712","url":null,"abstract":"<div>\u0000 \u0000 <p>Chirality has an important role in the drug design because enantiomers may exhibit different bioactivity when interacting with macromolecules of a living organism. In our previous work, based on the analysis of a set of 100 chiral drugs, a relationship was established between the sign of chirality of enantiomers and their bioactivity. To understand the reasons for the observed patterns of chiral specificity of drug enantiomers, the interaction of 10 enantiomeric pairs of chiral drugs with the corresponding target proteins has been considered using molecular docking and further postprocessing by quantum chemistry methods. The data obtained confirm that the energetic aspect of the interaction between opposite enantiomers and target protein affects the enantiomer biological activity. In addition, the results show that molecular docking is able to distinguish between bioactive and inactive/less active enantiomers, although many docking programs are not accurate enough to distinguish a weak inhibitor from a strong one.</p>\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 9","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142089836","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}
ChiralityPub Date : 2024-08-13DOI: 10.1002/chir.23702
Einat Bar, Rachel Davidovich-Rikanati, Shashank Saini, Moshe Inbar, Efraim Lewinsohn
{"title":"Chiral Chemopolymorphism in the Monoterpenes of Pistacia palaestina Leaves and Galls","authors":"Einat Bar, Rachel Davidovich-Rikanati, Shashank Saini, Moshe Inbar, Efraim Lewinsohn","doi":"10.1002/chir.23702","DOIUrl":"10.1002/chir.23702","url":null,"abstract":"<div>\u0000 \u0000 <p><i>Pistacia palaestina</i> Boiss. is a common tree in the Mediterranean maquis. The leaves of this plant accumulate defensive monoterpenes, whose levels greatly increase in galls induced by the aphid <i>Baizongia pistaciae</i>. We previously found a significant chemopolymorphism in monoterpene content among individual trees, but the chirality of these monoterpenes was unknown. Although most plant species specifically accumulate one enantiomeric form of a given compound, <i>P. palaestina</i> individuals display chemopolymorphism in the chirality of the key monoterpenes accumulated. We report here a marked enantiomeric variation for the limonene, α- and β-pinene, camphene, sabinene, δ-3-carene, and terpene-4-ol content in leaves and galls of nine different naturally growing <i>P. palaestina</i> trees. Interestingly, insect-induced gall monoterpene composition is an augmentation of the specific enantiopolymorphism originally displayed by each individual tree.</p>\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 8","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141975202","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":"Observation of the Liquid–Liquid Phase Separation of FUS-LC Using Vacuum-Ultraviolet Circular Dichroism Spectroscopy","authors":"Kentaro Fujii, Yudai Izumi, Nobuo Maita, Koichi Matsuo, Masato Kato","doi":"10.1002/chir.23707","DOIUrl":"10.1002/chir.23707","url":null,"abstract":"<div>\u0000 \u0000 <p>To reveal the structural mechanism by which the low-complexity domain of the fused in sarcoma protein (FUS-LC) mediates liquid–liquid phase separation (LLPS), we conducted a vacuum-ultraviolet circular dichroism (VUV-CD) spectroscopic study, a technique to analyze the secondary structures of proteins. The VUV-CD measurements were performed at the BL12 VUV-CD station at the Hiroshima Synchrotron Radiation Center (HiSOR) in Japan. CD spectra were measured between 180 and 260 nm while controlling the temperature of samples from 37°C to 5°C to obtain the LLPS of FUS-LC. The CD spectrum obtained at 37°C exhibited a large negative peak at 195 nm and a small negative shoulder near 220 nm. The peak intensity around 195 nm decreased as the sample temperature decreased. The spectral changes originated from the LLPS formation.</p>\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 8","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141916220","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":"Inherently Chiral Oligomers Based on Indole–Benzothiophene Core","authors":"Bartlomiej Bonczak, Sara Grecchi, Malinee Niamlaem, Gerardo Salinas, Roberto Cirilli, Serena Arnaboldi","doi":"10.1002/chir.23710","DOIUrl":"10.1002/chir.23710","url":null,"abstract":"<p>In recent years, transductors of chiral information based on conducting polymers have gained considerable attention. In particular, inherently chiral materials, which allow differentiation between the antipodes of a chiral analyte in terms of energetic variations, are highly desired. In this work, we successfully synthesized a novel inherently chiral oligomer based on an indole–benzothiophene core, namely, 2-([2,2′-bithiophen]-5-yl)-3-(2-([2,2′-bithiophen]-5-yl)benzo[<i>b</i>]thiophen-3-yl)-<i>N</i>-methylindole (BTIndT<sub>4</sub>). The electrochemical characterization evidences a stabilization of electrogenerated radical cations due to the presence of the indole group, which guides the oligomerization, producing well-ordered polymeric matrices. Furthermore, the in situ electrochemical conductance analysis demonstrates a simultaneous intrachain and interchain transfer of charge carriers. Finally, the highly efficient enantiorecognition capabilities of the antipodes of the oligo-BTIndT<sub>4</sub> films toward the enantiomers of tryptophan and 3,4-dihydroxyphenylalanine (DOPA), as model chiral analytes, were demonstrated.</p>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 8","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chir.23710","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141896942","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":"Enantiomeric Analysis of Chiral Drugs Using Mass Spectrometric Methods: A Comprehensive Review","authors":"Bhaskar Vallamkonda, Sonika Sethi, PhanikumarReddy Satti, Dipak Kumar Das, Suman Yadav, Vinod Kumar Vashistha","doi":"10.1002/chir.23705","DOIUrl":"10.1002/chir.23705","url":null,"abstract":"<div>\u0000 \u0000 <p>Chirality plays a crucial role in the drug development process, influencing fundamental chemical and biochemical processes and significantly affecting our daily lives. This review provides a comprehensive examination of mass spectrometric (MS) methods for the enantiomeric analysis of chiral drugs. It thoroughly investigates MS-hyphenated techniques, emphasizing their critical role in achieving enantioselective analysis. Furthermore, it delves into the intricate chiral recognition mechanisms inherent in MS, elucidating the fundamental principles that govern successful chiral separations. By critically assessing the obstacles and potential benefits associated with each MS-based method, this review offers valuable insights for researchers navigating the complexities of chiral analysis. Both qualitative and quantitative approaches are explored, presenting a comparative analysis of their strengths and limitations. This review is aimed at significantly enhancing the understanding of chiral MS methods, serving as a crucial resource for researchers and practitioners engaged in enantioselective studies.</p>\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 8","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141892995","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}