Chirality最新文献

{"title":"New methods for resolution of hydroxychloroquine by forming diastereomeric salt and adding chiral mobile phase agent on RP-HPLC","authors":"Chen Chen, Yangfeng Peng, Yongming Wei, Mengyuan Liu, Yu Wang, Siqi Xiong, Huiyi Li, Quan He","doi":"10.1002/chir.23672","DOIUrl":"https://doi.org/10.1002/chir.23672","url":null,"abstract":"<p>Hydroxychloroquine (HCQ), 2-([4-([7-Chloro-4-quinolyl]amino)pentyl]ethylamino)ethanol, exhibited significant biological activity, while its side effects cannot be overlooked. The RP-HPLC enantio-separation was investigated for cost-effective and convenient optical purity analysis of HCQ. The thermodynamic resolution of Rac-HCQ, driven by enthalpy and entropy, was achieved on the C18 column using Carboxymethyl-β-cyclodextrin (CM-β-CD) as the chiral mobile phase agent (CMPA). The effects of C<sub>CM-β-CD</sub>, pH, and triethylamine (TEA) V% on the enantio-separation process were explored. Under the optimum conditions at 24°C, the retention times for the two enantiomers were <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <msub>\u0000 <mi>t</mi>\u0000 <mrow>\u0000 <mi>R</mi>\u0000 <mn>1</mn>\u0000 </mrow>\u0000 </msub>\u0000 <mo>=</mo>\u0000 <mn>29.39</mn>\u0000 <mspace></mspace>\u0000 <mi>min</mi>\u0000 </mrow>\u0000 <annotation>$$ {t}_{R1}=29.39 min $$</annotation>\u0000 </semantics></math> and <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <msub>\u0000 <mi>t</mi>\u0000 <mrow>\u0000 <mi>R</mi>\u0000 <mn>2</mn>\u0000 </mrow>\u0000 </msub>\u0000 <mo>=</mo>\u0000 <mn>32.42</mn>\u0000 <mspace></mspace>\u0000 <mi>min</mi>\u0000 </mrow>\u0000 <annotation>$$ {t}_{R2}=32.42 min $$</annotation>\u0000 </semantics></math>, resulting in <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <msub>\u0000 <mi>R</mi>\u0000 <mi>s</mi>\u0000 </msub>\u0000 <mo>=</mo>\u0000 <mn>1.87</mn>\u0000 </mrow>\u0000 <annotation>$$ {R}_s=1.87 $$</annotation>\u0000 </semantics></math>. The resolution via diastereomeric salt formation of Rac-HCQ was developed to obtain the active pharmaceutical ingredient of single enantiomer S-HCQ. Di-p-Anisoyl-L-Tartaric Acid (L-DATA) was proved effective as the resolution agent for Rac-HCQ. Surprisingly, it was found that refluxing time was a key fact affecting the resolution efficiency, which meant the kinetic dominate during the process of the resolution. Four factors—solvent volume, refluxing time, filtration temperature, and molar ratio—were optimized using the single-factor method and the response surface method. Two cubic models were established, and the reliability was subsequently verified. Under the optimal conditions, the less soluble salt of 2L-DATA:S-HCQ was obtained with a yield of 96.9% and optical purity of 63.0%. The optical purity of this less soluble salt increases to 99.0% with a yield of 74.2% after three ","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 5","pages":""},"PeriodicalIF":2.0,"publicationDate":"2024-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140818992","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":"Asymmetric catalysis by chiral FLPs: A computational mini-review","authors":"Shanti Gopal Patra","doi":"10.1002/chir.23671","DOIUrl":"https://doi.org/10.1002/chir.23671","url":null,"abstract":"<p>Steric hindrance in Lewis acid (LA) and Lewis base (LB) obstruct the Lewis acid–base adduct formation, and the pair was termed as frustrated Lewis pair (FLP). In the past 16 years, the field of enantioselective catalysis by chiral FLPs has been slowly growing. It was shown that chiral LAs are significant as they are involved in the hydrogen transfer (HT) step to the imine, resulting in enantioselectivity. After H₂ activation, the borohydride can exist in a number of plausible conformations and their stability is governed by the presence of noncovalent interaction through C–H····π and π····π interactions. However, LBs are not ideal for asymmetric induction as they compete with the imine substrate as a counter LB. Further, the proton transfer from chiral LB to the imine does not induce any chirality as chirality develops in the HT step. However, intramolecular FLPs with chiral scaffold are very efficient as they possess an optimum distance between LA and LB, which facilitates the H₂ activation but precludes the adduct formation of the small molecules substrate with the LA component. This mini-review summarizes computational investigation involving chiral LA and LB, and discusses intramolecular FLPs in the enantioselective catalysis.</p>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 5","pages":""},"PeriodicalIF":2.0,"publicationDate":"2024-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140641768","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":"Advantages of a synchrotron light source for fluorescence-detected linear dichroism","authors":"Nykola C. Jones,&nbsp;Alison Rodger,&nbsp;Søren V. Hoffmann","doi":"10.1002/chir.23667","DOIUrl":"https://doi.org/10.1002/chir.23667","url":null,"abstract":"<p>Fluorescence-detected linear dichroism (FD-LD) enables one to collect linear dichroism spectra for oriented fluorophores in the presence of other absorbing species and light scattering. The experiment proceeds by scanning the excitation wavelength and using a filter to collect only emitted photons from the fluorophore. Thus, it has the potential to give data with enhanced selectivity and quality. By using a synchrotron radiation light source and fluorescence-detection, we show data for a range of fluorophores in different orienting environments. Film and flow-oriented FD-LD spectra were collected down to 170 nm. Even for flow-oriented liposomes, we have data collected down to 210 nm. For strongly scattering samples, for example, liposomes, FD-LD has the clear advantage that scattering is absent for the longer wavelength fluorescence photons. The collimated and smaller beam size of the synchrotron radiation also gives rise to sharper and more well-defined features in the spectra.</p>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 4","pages":""},"PeriodicalIF":2.0,"publicationDate":"2024-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chir.23667","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140550032","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":"Novel ethylenediamine-β-cyclodextrin grafted membranes for the chiral separation of mandelic acid and its derivatives","authors":"Junjie Zhou,&nbsp;Yongming Wei,&nbsp;Jiaojie Wu,&nbsp;Shuqin Li,&nbsp;Zhenliang Xu,&nbsp;Yangfeng Peng","doi":"10.1002/chir.23662","DOIUrl":"https://doi.org/10.1002/chir.23662","url":null,"abstract":"<p>In the present study, flat cellulose acetate ultrafiltration membranes were prepared first by nonsolvent induced phase separation method. Then chiral membranes for separating the enantiomers were prepared by grafting the ultrafiltration membranes using ethylenediamine-β-cyclodextrin as the chiral selector and epichlorohydrin as the spacer arm. The pure water permeability of the ultrafiltration membrane was around 115 L·m⁻²·h⁻¹·bar⁻¹. The properties of the chiral membranes were characterized using infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The chiral membrane performance in enantiomer separation was evaluated with racemates, such as mandelic acid (MA), 2-chloromandelic acid (2-ClMA), 4-chloromandelic acid (4-ClMA), and methyl mandelate (MM). The influence of feed concentration on the separation efficiency was also investigated. The results indicated that the enantiomeric excess percentages (e.e%) of the racemic mixtures for these four chiral compounds were up to 31.8%, 25.4%, 17.8%, and 32.6%, respectively. The binding free energy of the chiral selector with the (<i>S</i>)-enantiomer calculated by molecular dynamics simulations was stronger than that with the (<i>R</i>)-enantiomer, which was consistent with the experimental results (higher concentration of (<i>R</i>)-enantiomer in the permeate). This supports the affinity absorption-separation mechanism.</p>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 4","pages":""},"PeriodicalIF":2.0,"publicationDate":"2024-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140345718","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":"Preparation of amino acid chiral ionic liquid and visual chiral recognition of glutamine and phenylalanine enantiomers","authors":"Luzheng Dong,&nbsp;Jun Wu,&nbsp;Xiashi Zhu","doi":"10.1002/chir.23665","DOIUrl":"https://doi.org/10.1002/chir.23665","url":null,"abstract":"<p>In this paper, the amino acid chiral ionic liquid (AACIL) was prepared with L-phenylalanine and imidazole. It was characterized by CD, FT-IR, ¹H NMR, and ¹³C NMR spectrum. The chiral recognition sensor was constructed with AACIL and Cu(II), which exhibited different chiral visual responses (solubility or color difference) to the enantiomers of glutamine (Gln) and phenylalanine (Phe). The effects of solvent, pH, time, temperature, metal ions, and other amino acids on visual chiral recognition were optimized. The minimum concentrations of Gln and Phe for visual chiral recognition were 0.20 mg/ml and 0.28 mg/ml, respectively. The mechanism of chiral recognition was investigated by FT-IR, TEM, SEM, TG, XPS, and CD. The location of the host-guest inclusion or molecular placement has been conformationally searched based on Gaussian 09 software.</p>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 4","pages":""},"PeriodicalIF":2.0,"publicationDate":"2024-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140345743","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":"Separation of enantiomers of chiral fullerene derivatives through enantioselective encapsulation within an adaptable helical cavity of syndiotactic poly(methyl methacrylate) with helicity memory","authors":"Daisuke Taura,&nbsp;Akiko Minami,&nbsp;Fumihiko Mamiya,&nbsp;Naoki Ousaka,&nbsp;Kenichiro Itami,&nbsp;Eiji Yashima","doi":"10.1002/chir.23663","DOIUrl":"10.1002/chir.23663","url":null,"abstract":"<p>Optically active left (<i>M</i>)- and right (<i>P</i>)-handed helical syndiotactic poly(methyl methacrylate)s (<i>M</i>- and <i>P</i>-st-PMMAs) with a helicity memory enantioselectively encapsulated the racemic C₆₀ derivatives, such as 3,4-fulleroproline <i>tert</i>-butyl ester (<i>rac</i>-<b>1</b>) and tetraallylated C₆₀ (<i>rac</i>-<b>2</b>), as well as the C₆₀-bound racemic 3₁₀-helical peptides (<i>rac</i>-<b>3</b>) within their helical cavities to form peapod-like inclusion complexes and a unique “helix-in-helix” superstructure, respectively. The enantiomeric excess (ee) and separation factor (enantioselectivity) (<i>α</i>) of the analyte <b>1</b> (ee = 23%–25% and <i>α</i> = 2.35–2.50) encapsulated within the helical cavities of the <i>M</i>- and <i>P</i>-st-PMMAs were higher than those of the analytes <b>2</b> and <b>3</b> (ee = 4.3%–6.0% and <i>α</i> = 1.28–1.50). The optically pure (<i>S</i>)- and (<i>R</i>)-<b>1</b> were found to more efficiently induce an excess one-handed helical conformation in the st-PMMA backbone than the optically pure (<i>S</i>)- and (<i>R</i>)-1-phenylethylamine, resulting in intense mirror-image vibrational circular dichroism (VCD) spectra in the PMMA IR regions. The excess one-handed helices induced in the st-PMMAs complexed with (<i>S</i>)- and (<i>R</i>)-<b>1</b> were memorized after replacement with the achiral C₆₀, and the complexes exhibited induced electric CDs in the achiral C₆₀ chromophore regions.</p>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 4","pages":""},"PeriodicalIF":2.0,"publicationDate":"2024-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140334880","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":"Linear dichroism reveals the perpendicular orientation of DNA bases in the RecA and Rad51 recombinase filaments: A possible mechanism for the strand exchange reaction","authors":"Masayuki Takahashi,&nbsp;Kentaro Ito,&nbsp;Hiroshi Iwasaki,&nbsp;Bengt Norden","doi":"10.1002/chir.23664","DOIUrl":"10.1002/chir.23664","url":null,"abstract":"<p>Linear dichroism spectroscopy is used to investigate the structure of RecA family recombinase filaments (RecA and Rad51 proteins) with DNA for clarifying the molecular mechanism of DNA strand exchange promoted by these proteins and its activation. The measurements show that the recombinases promote the perpendicular base orientation of single-stranded DNA only in the presence of activators, indicating the importance of base orientation in the reaction. We summarize the results and discuss the role of DNA base orientation.</p>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 4","pages":""},"PeriodicalIF":2.0,"publicationDate":"2024-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140334879","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":"Biocatalytic enantioselective synthesis of cenobamate, an antiepileptic drug","authors":"Vennapusa Haritha,&nbsp;Pulivarthi Deepthi,&nbsp;Rachel Gundamalla,&nbsp;Kommu Nagesh,&nbsp;Suggala V. Satyanarayana,&nbsp;Adari Bhaskar Rao,&nbsp;Sridhar Balasubramanian,&nbsp;Basireddy Venkata Subba Reddy","doi":"10.1002/chir.23660","DOIUrl":"10.1002/chir.23660","url":null,"abstract":"<p>A green and efficient process for the synthesis of cenobamate has been accomplished in 70% yield and &gt;99% ee through the bio-reduction of <i>β</i>-ketotetrazole using <i>Daucus carota</i> whole plant cells. The corresponding <i>β</i>-hydroxytetrazole was isolated in 60% yield and &gt;98% ee. This is the first report on the biocatalytic reduction of <i>β</i>-ketotetrazole using plant enzymes derived from <i>D. carota</i> root cells with excellent enantioselectivity.</p>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 4","pages":""},"PeriodicalIF":2.0,"publicationDate":"2024-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140173878","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":"Simultaneous identification and enantioseparation of ofloxacin and duloxetine without the single standard and computational calculation of their inclusion complexes","authors":"Lixia Chen,&nbsp;Xiangjun Li","doi":"10.1002/chir.23661","DOIUrl":"10.1002/chir.23661","url":null,"abstract":"<p>Given the markedly different pharmacological activities between enantiomeric isomers, it is crucial to encourage the stereoselective determination of chiral drugs in the biological and pharmaceutical fields, and the combination of drugs makes this analysis more complicated and challenging. Herein, a capillary electrophoresis (CE) method for the enantioseparation of ofloxacin and duloxetine was established, enabling the simultaneous identification of four isomers in nonracemic mixtures with enantiomeric excess (ee%) values exceeding 5%. This was achieved through the integration of theoretical simulation and electron circular dichroism (ECD), all without reliance on individual standards. Molecular modeling explained and verified the migration time differences of these isomers in electrophoretic separation. Moreover, the correlation coefficients (<i>R</i>²) between the enantiomeric peak area differentials and ee% were both above 0.99. Recovery rates were quantified using bovine serum as the matrix, with results ranging from 93.32% to 101.03% (RSD = 0.030) and 92.69% to 100.52% (RSD = 0.028) for these two chiral drugs at an ee value of 23.1%, respectively.</p>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 3","pages":""},"PeriodicalIF":2.0,"publicationDate":"2024-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140058846","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":"Enantiomeric separation of thiourea derivatives of naringenin on amylose and cellulose polymeric chromatographic chiral columns","authors":"Imran Ali,&nbsp;Rekia Nabti,&nbsp;Nasser Belboukhari,&nbsp;Khaled Sekkoum,&nbsp;Mohammed El Amin Zaid,&nbsp;Khairedine Kraim,&nbsp;Zeid A. ALOthman,&nbsp;Marcello Locatelli,&nbsp;Ersin Demir","doi":"10.1002/chir.23659","DOIUrl":"10.1002/chir.23659","url":null,"abstract":"<p>Due to a great demand for amylose and cellulose polymeric chromatographic chiral columns, the enantiomeric separation of thiourea derivatives of naringenin was achieved on the different amylose (Chiralpak-IB) and cellulose chiral (Chiralcel-OJ and Chiralcel-OD-3R) columns with varied chromatographic conditions. The isocratic mobile phases used were ethanol and methanol, where ethanol/hexane and methanol/hexane were used as gradient mode and were prepared in volume/volume relation. The separation and resolution factors for all the enantiomers were in the range of 1.25 to 3.47 and 0.48 to 1.75, respectively. The enantiomeric resolution was obtained within 12 min making fast separation. The docking studies confirmed the chiral recognition mechanisms with binding affinities in the range of −4.7 to −5.7 kcal/mol. The reported compounds have good anticoagulant activities and may be used as anticoagulants in the future. Besides, chiral separation is fast and is useful for enantiomeric separation in any laboratory in the world.</p>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 3","pages":""},"PeriodicalIF":2.0,"publicationDate":"2024-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140038863","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}