ChiralityPub Date : 2024-10-24DOI: 10.1002/chir.70002
F. Safia Kariapper, Flavia Miccolis, Samantha L. Pilicer, Christian Wolf
{"title":"Chiroptical Sensing of Amines With Isatins","authors":"F. Safia Kariapper, Flavia Miccolis, Samantha L. Pilicer, Christian Wolf","doi":"10.1002/chir.70002","DOIUrl":"10.1002/chir.70002","url":null,"abstract":"<div>\u0000 \u0000 <p>Isatins are extensively researched compounds with diverse applications, particularly as synthetic precursors in pharmaceutical developments. However, their use as optical probes for enantioselective sensing of chiral amines has not been explored to date. Herein, we present a novel chiroptical assay with an optimized isatin that generates strong, red-shifted circular dichroism (CD) signals at approximately 380 nm upon ketimine formation with chiral amines. The intensity of the induced CD signal increases linearly with the enantiomeric excess of the analyte and thus allows quantitative chirality analysis. The general usefulness of this approach is demonstrated with a broad range of aliphatic and aromatic chiral amines, and by accurate determination of the enantiomeric composition of 10 samples.</p>\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 11","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142496116","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 : 2024-10-22DOI: 10.1002/chir.70000
Fan Jiang, Ke-Xin Chen, Jiang-Mei Xiang, Yong-Cun Shen
{"title":"An Enzymatic Method to Obtain Enantiopure 3-Pyridyl and Substituted Phenyl Alanine","authors":"Fan Jiang, Ke-Xin Chen, Jiang-Mei Xiang, Yong-Cun Shen","doi":"10.1002/chir.70000","DOIUrl":"10.1002/chir.70000","url":null,"abstract":"<div>\u0000 \u0000 <p>Chiral phenylalanine derivatives are important raw materials and building blocks for the synthesis of peptides and drug molecules. Enantiomerically pure <i>D/L</i>-3-pyridyl- and phenylalanine has shown wide application potential in the synthesis of various drug intermediates. This article focuses on two synthetic routes from different feedstocks. The first approach is an Erlenmeyer–Plöchl route study using <i>N</i>-acetylglycine as starting material, whereas the second is an alkylation route study using diethyl acetamidomalonate as starting material. The key step is the resolution of <i>N</i>-acetamido-alanine esters using different quantities of fairly inexpensive Protamex proteinase to obtain pure enantiomeric <i>D/L</i>-3-pyridyl- and substituted phenylalanine or its derivative, with the ee value and purity of all products exceeding 99%. The different chiral arylalanine derivatives that can be prepared using the above two methods have good versatility.</p>\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 11","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142459351","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 : 2024-10-15DOI: 10.1002/chir.23722
Mohamed I. A. Ibrahim, Mahmoud E. Esmael, Tamer R. Elmashi, Tatsuki Haga, Reda A. Bayoumi, Mohamed M. Eldanasoury, Mahmoud R. Sofy, Koichi Matsuo, Abdelrahman M. Khattab
{"title":"Structure Assessment and Impacts of Lipids' Chemistry on the Structuration of Polyhydroxyalkanoate Biosynthesized by Bacillus licheniformis AZU-A5","authors":"Mohamed I. A. Ibrahim, Mahmoud E. Esmael, Tamer R. Elmashi, Tatsuki Haga, Reda A. Bayoumi, Mohamed M. Eldanasoury, Mahmoud R. Sofy, Koichi Matsuo, Abdelrahman M. Khattab","doi":"10.1002/chir.23722","DOIUrl":"https://doi.org/10.1002/chir.23722","url":null,"abstract":"<p>The current study exploited cheese whey supernatant (CWS) as a renewable resource for polyhydroxyalkanoates (PHAs) formation. Structure identification and investigating the influence of lipid membranes' chemistry on PHA structuration were detailed. Approximately 66 bacterial isolates from dairy products companies in Egypt were screened for PHA production, and the bacterial isolate AZU-A5, identified as <i>Bacillus licheniformis</i> strain AZU-A5, showed the highest production PHA 0.93 g L<sup>−1</sup>) using whey lactose. The highest PHA rate in the individual design was 1.59 g L<sup>−1</sup> with a recovery yield of 33.08% (w w<sup>−1</sup>), while the production rate in the statistical design reached 1.75 g L<sup>−1</sup> PHA and 51.60% PHA content. Structurally, the PHA was identified as polyhydroxy-3R-butyrate (R-PH3B). The fibrous texture by SEM highlighted the self-assembly of PHB. The CD analysis of the PHA films suggested favorable hydrophobic interactions between lipids and PHB. Higher lipid contents not only caused a decrement in the CD signal of PHB but also bathochromic effects occurred. The chain length of lipids exerted high impacts on interactions (CD) and structuration of PHB (Δλ). The unsaturation showed little influence on CD and negligible effect on Δλ, while the head group exerted no effect on CD with a considerable impact on Δλ.</p>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 10","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chir.23722","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142443375","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 : 2024-10-15DOI: 10.1002/chir.23719
Masashi Hatanaka
{"title":"Optical Activities of Organic Crystals: Crystal Orbital Formulation of Anisotropic Gyration","authors":"Masashi Hatanaka","doi":"10.1002/chir.23719","DOIUrl":"https://doi.org/10.1002/chir.23719","url":null,"abstract":"<div>\u0000 \u0000 <p>To describe the optical activities of crystals, gyration tensors are necessary for all wavelengths of incident light. To date, few studies on direct calculations of gyration tensors from Bloch states have been conducted. Herein, a practical procedure to obtain gyration tensors of organic crystals is presented using the crystal orbital method. The extended Hückel method was adopted to evaluate the gyration tensors, epitomizing the one-electron formulation. To confirm the validity of the formulation, the optical rotatory power of alanine and <i>γ</i>-glycine was examined. The reproduced profiles of the optical rotatory power were consistent with the results of recent experiments. This is a general formulation of the one-electron theory of optical activities for three-dimensional crystals. In principle, the optical rotatory strength tensor is not invariant with translation. For systems with small unit cells, however, the formalism is quasi-invariant with respect to translation. The quasi origin-independent formalism is sufficiently substantial to be applicable to modern crystal optics.</p>\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 10","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142443374","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 : 2024-10-13DOI: 10.1002/chir.23723
Chiriki Devi Sri, Syed Faizan, Muttavarapu Rohit Chandra, B. R. Prashantha Kumar, B. M. Gurupadayya
{"title":"Enantioselective Separation and Pharmacokinetics of a Chiral 1,4-Dihydropyrimidine Derivative in Rats: A Combined Chromatography and Docking Approach","authors":"Chiriki Devi Sri, Syed Faizan, Muttavarapu Rohit Chandra, B. R. Prashantha Kumar, B. M. Gurupadayya","doi":"10.1002/chir.23723","DOIUrl":"https://doi.org/10.1002/chir.23723","url":null,"abstract":"<div>\u0000 \u0000 <p>Chirality in 1,4-Dihydropyrimidines influences their pharmacological properties and synthetic strategies. Enantiomers of chiral drugs often exhibit different pharmacokinetic profiles. Therefore, separating and studying individual enantiomers is crucial to optimize drug efficacy and safety. Enantiomeric separation of ±4-(4-chlorophenyl)-6-methyl-2-oxo-N-(O-toyl)-1,2,3,4-tetrahydropyrimidine-5-carboxamide (DP-1), which is a 1,4-Dihydropyrimidine derivative is achieved on CHIRALCEL® OD-H column (particle size: 5 μm, inner diameter: 4.6 mm, length:150 mm), following by investigating the kinetic properties of (R) and (S) enantiomers. The separation was achieved with a mobile phase composed of 70% (v/v) isopropyl alcohol and 30% (v/v) n-hexane. For the bioanalytical study, acetonitrile was used to precipitate the rat plasma samples and validated the method according to USFDA guidelines. The validated bioanalytical method was then successfully applied to determine the pharmacokinetic parameters of the drug in biological samples. Molecular modeling techniques, specifically docking simulations, were employed to predict the elution order of DP-1 enantiomers. The docking results revealed moderate binding interactions between the enantiomers and the chiral stationary phase (CSP), which aligns with the theoretical expectation that stronger interactions lead to longer retention times on the column.</p>\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 10","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142435688","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":"Chiral Self-Sorting Process With C2 Symmetric Bisimidazoline Ligands","authors":"Caitlyn Dussart, Aline Maisse-François, Stéphane Bellemin-Laponnaz","doi":"10.1002/chir.23720","DOIUrl":"10.1002/chir.23720","url":null,"abstract":"<p>We have studied the coordination chemistry of chiral imidazoline-based <i>C</i><sub>2</sub>-symmetric ligands with zinc (II) and copper (II). Two types of bisimidazoline ligands were studied, one with the free amine (BIM-H) and the other with the amine protected by a toluene sulfonyl group in position 6 (BIM-Ts). The complexes formed were isolated, purified, and characterized, in particular by X-ray diffraction studies and CD in the case of the enantiopure complexes. By playing with the choice of ligand system (enantiopure or racemate), we were able to show that the selective formation of homoleptic and heteroleptic metal complexes can be controlled by means of the chiral molecular instruction of bisimidazoline ligands.</p>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 10","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chir.23720","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142399567","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":"Determination of Ibuprofen Enantiomers in Mouse Blood Using Liquid Chromatography–Tandem Mass Spectrometry and Its Application to a Pharmacokinetic Study","authors":"Yuexin Li, Jinglai Li, Huanhuan Yang, Huan Luo, Shiqi Liu, Furong Han, Zhipeng Ruan, Zhili Xiong","doi":"10.1002/chir.23721","DOIUrl":"10.1002/chir.23721","url":null,"abstract":"<div>\u0000 \u0000 <p>The aim of this study was to establish a simple, fast, and sensitive method with liquid chromatography–tandem mass spectrometry (LC–MS/MS) for simultaneously determining ibuprofen enantiomers using mouse blood in very small volumes. LC–MS/MS equipped with an electrospray ionization (ESI) source was used in negative ion mode and multiple-reaction monitoring mode. Enantiomer chromatographic separation was carried out on a Lux® 5 μm Cellulose-3 (250 × 4.6 mm, 5 μm) column at a flow rate of 0.6 mL/min. Samples were pretreated by extracting only 5 μL of blood with 40 μL of acetonitrile (containing 1.3% formic acid) so that a concentration-time profile could be completed using a single mouse. 2-(4-Propylphenyl) propanoic acid was used as an internal standard. Standard curves for each enantiomer were linear from 0.04 to 80.00 μg/mL, demonstrating a lower limit of quantitation (LLOQ) than all previously reported methods. This method was completely validated and successfully executed to investigate the pharmacokinetics of ibuprofen enantiomers after intravenous administration of racemic ibuprofen, (S)-(+)-ibuprofen, and (R)-(−)-ibuprofen in Kunming mice, respectively. The results showed that the pharmacokinetic profiles of the (R)-(−)-ibuprofen and (S)-(+)-ibuprofen were significantly different, indicating the unidirectional inversion of R-(−)-ibuprofen to (S)-(+)-ibuprofen.</p>\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 10","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142388475","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 : 2024-10-01DOI: 10.1002/chir.23716
Daniel Vasiliev, Shay Tirosh, Assaf Ben-Moshe
{"title":"Experimental Determination of the Chiral and Achiral Shape Diagrams of Tellurium Nanocrystals","authors":"Daniel Vasiliev, Shay Tirosh, Assaf Ben-Moshe","doi":"10.1002/chir.23716","DOIUrl":"10.1002/chir.23716","url":null,"abstract":"<p>The interface between chirality and crystallization and mechanisms by which chirality propagates from crystal structure to overall shapes of crystals are a key topic in crystallography and stereochemistry. Recently, nanocrystals attracted attention as useful model systems for this kind of studies. Specifically, tellurium nanocrystals have been used to address questions on relations between chirality of the crystal structure and that of the overall shape. Previous studies of this system did not offer a comprehensive shape diagram and did not survey all the factors that determine whether shapes that form are chiral or not. In the current report, the distribution of chiral and achiral shapes in this system as a function of different physical and chemical parameters is determined experimentally. It is shown that there is a common logic for formation of chiral shapes, that is, growth at conditions that favor the growth of more reactive nuclei. The experiments also reveal more morphologies than previously encountered, suggesting that a systematic change of conditions in nanocrystal growth is key for identifying morphologies that exist only in a narrow range of conditions.</p>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 10","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chir.23716","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142364594","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 : 2024-09-24DOI: 10.1002/chir.23718
Yui Nagase, Yoshiki Naka, Tatsuo Nehira
{"title":"6-Methoxy-2-Naphthoate as a Standard Chromophore for Chiroptical Studies by Fluorescence-Detected Exciton-Coupled Circular Dichroism","authors":"Yui Nagase, Yoshiki Naka, Tatsuo Nehira","doi":"10.1002/chir.23718","DOIUrl":"https://doi.org/10.1002/chir.23718","url":null,"abstract":"<p>This study investigated the applicability of fluorescent chromophores for exciton-coupled circular dichroism (ECCD) exploiting fluorescence-detected circular dichroism (FDCD). FDCD had been previously reported useful in allowing the sensitive detection of ECCD in favorable conditions. However, fluorescence detection may prevent applications of the combined method especially when solutions are polarized in emission. Even without polarization of emission, FDCD deviates from circular dichroism (CD) in some cases when the fluorophore of interest interacts with nonfluorescent chromophore. Herein, it was confirmed that employing 6-methoxy-2-naphthoate always yielded interpretable exciton-coupled FDCD spectra even when coupling with nonfluorescent <i>p</i>-substituted benzoates. The 6-methoxy-2-naphthoate chromophore (6-MN) is prescribed in special cases when only a small amount of sample is available for determining the absolute stereochemistry by the CD exciton chirality method observed by FDCD.</p>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 10","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chir.23718","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142320588","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 : 2024-09-15DOI: 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}