Literatura académica sobre el tema "Chiral ions pair"

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Artículos de revistas sobre el tema "Chiral ions pair"

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Smith, Owen, Mihai V. Popescu, Madeleine J. Hindson, Robert S. Paton, Jonathan W. Burton y Martin D. Smith. "Control of stereogenic oxygen in a helically chiral oxonium ion". Nature 615, n.º 7952 (15 de marzo de 2023): 430–35. http://dx.doi.org/10.1038/s41586-023-05719-z.

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AbstractThe control of tetrahedral carbon stereocentres remains a focus of modern synthetic chemistry and is enabled by their configurational stability. By contrast, trisubstituted nitrogen1, phosphorus2 and sulfur compounds3 undergo pyramidal inversion, a fundamental and well-recognized stereochemical phenomenon that is widely exploited4. However, the stereochemistry of oxonium ions—compounds bearing three substituents on a positively charged oxygen atom—is poorly developed and there are few applications of oxonium ions in synthesis beyond their existence as reactive intermediates5,6. There are no examples of configurationally stable oxonium ions in which the oxygen atom is the sole stereogenic centre, probably owing to the low barrier to oxygen pyramidal inversion7 and the perception that all oxonium ions are highly reactive. Here we describe the design, synthesis and characterization of a helically chiral triaryloxonium ion in which inversion of the oxygen lone pair is prevented through geometric restriction to enable it to function as a determinant of configuration. A combined synthesis and quantum calculation approach delineates design principles that enable configurationally stable and room-temperature isolable salts to be generated. We show that the barrier to inversion is greater than 110 kJ mol−1 and outline processes for resolution. This constitutes, to our knowledge, the only example of a chiral non-racemic and configurationally stable molecule in which the oxygen atom is the sole stereogenic centre.
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Mercea, Dan M., Michael G. Howlett, Adam D. Piascik, Daniel J. Scott, Alan Steven, Andrew E. Ashley y Matthew J. Fuchter. "Enantioselective reduction of N-alkyl ketimines with frustrated Lewis pair catalysis using chiral borenium ions". Chemical Communications 55, n.º 49 (2019): 7077–80. http://dx.doi.org/10.1039/c9cc02900a.

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Karlsson, Anders y Olle Karlsson. "Chiral ion-pair chromatography on porous graphitized carbon using N-blocked dipeptides as counter ions". Journal of Chromatography A 905, n.º 1-2 (enero de 2001): 329–35. http://dx.doi.org/10.1016/s0021-9673(00)00986-9.

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Sellmann, Dieter, Helge Friedrich y Falk Knoch. "Übergangsmetallkomplexe mit Schwefelliganden, XCIX. Bildung und Struktur von [Fe(′S4′)]4. Eine bemerkenswerte Tetramerisierung homochiraler[Fe(′S4′)]-Komplexfragmente (′S4′2- = 1,2-Bis(2-mercaptophenylthio)ethan(2-)) / Transition Metal Complexes with Sulfur Ligands, XCIX. Formation and Structure of [Fe(′S4′)]4. A Remarkable Tetramerization of Homochiral [Fe(′S4′)] Complex Fragments (′S4′2-= 1,2-Bis(2-mercaptophenylthio)ethane(2–))". Zeitschrift für Naturforschung B 48, n.º 11 (1 de noviembre de 1993): 1675–80. http://dx.doi.org/10.1515/znb-1993-1128.

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In MeOH/THF solution, Fe(II) ions and the tetradentate thioether-thiolate ′S4′2-([1,2-Bis(2-mercaptophenylthio)ethane(2-)]) slowly form the tetrameric [Fe(′S4′)]4 1. The crystal structure of 1 · THF • 2 MeOH was determined by X-ray structure analysis. Chiral 1 crystallizes as a pair of enantiomers each of which consist of four homochiral [Fe(′S4′)] fragments bridged via μ2- and µ3-S(thiolato) donors; stereochemical aspects of the enantiospecific tetramerization of [Fe(′S4′)] fragments are discussed. In strong polar solvents such as dimethylformamide, dissociation of [Fe(′S4′)]4 into [Fe(′S4′)]2 fragments is indicated by the formation of [Fe(CO)(′S4′)]2 upon reaction with CO.
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Wang, Hai-Ping, Shao-Yun Yin, Mei Pan, Kai Wu, Ling Chen, Yi-Xuan Zhu y Ya-Jun Hou. "Circular dichroism enhancement by the coordination of different metal ions with a pair of chiral tripodal ligands". Inorganic Chemistry Communications 54 (abril de 2015): 92–95. http://dx.doi.org/10.1016/j.inoche.2015.02.013.

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Tsunematsu, Hideaki, Hirohito Ikeda, Hiroshi Hanazono, Masanori Inagaki, Ryuichi Isobe, Ryuichi Higuchi, Yoshinobu Goto y Magobei Yamamoto. "Differentiation of a pair of diastereomeric tertiarybutoxycarbonylprolylproline ethyl esters by collision-induced dissociation of sodium adduct ions in electrospray ionization mass spectrometry and evidence for chiral recognition byab initio molecular orbital calculations". Journal of Mass Spectrometry 38, n.º 2 (2003): 188–95. http://dx.doi.org/10.1002/jms.428.

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BARSHAY, SAUL. "ARE NARROW POSITRON-ELECTRON LINES CREATED BY DECAY OF EXCITED VACUUM-LIKE SYSTEMS FORMED FROM A COHERENT PIONIC PHASE PRESENT IN HEAVY-ION COLLISIONS?" Modern Physics Letters A 07, n.º 20 (28 de junio de 1992): 1843–53. http://dx.doi.org/10.1142/s0217732392001555.

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A novel description of several narrow, correlated electron-positron lines observed in heavy-ion collisions, arises from a physical picture involving the decay of a group of related, excited coherent bosonic states, which resemble an excited, chira σ vacuum-condensate. These systems are formed in the collision of a coherent pionic phase present in the heavy ions. Further experimental tests of the idea, involve the specific form of the opening angle correlation between the positron-electron pair, and possibly, the nature of the charge states of the final-state ions.
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Tao, Kezheng, Qiang Li y Qingfeng Yan. "1D Tin(II)‐Based Chiral Hybrid Perovskite Single Crystals with Extremely Distorted Inorganic Chains for Second Harmonic Generation". Advanced Optical Materials, 17 de febrero de 2024. http://dx.doi.org/10.1002/adom.202400018.

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AbstractThe organic–inorganic hybrid metal halides with chiral structures have attracted great attentions in the field of optoelectronic functional materials, especially for nonlinear optics. To date, second harmonic generation (SHG) properties of several classes of chiral hybrid halides with different metal ions have been reported. However, SHG‐active tin(II)‐based chiral materials are rarely explored, hindering deep understandings of the relationship between their structures and SHG properties. Herein, Sn2+ ions are successfully introduced into chiral hybrid perovskites, and four new species of chiral hybrid perovskites (R/S‐α‐PEA)SnX3 (X = Cl and Br, PEA = phenylethylammonium) are obtained. The as‐grown crystals are in P212121 space group, with highly distorted [SnX6] octahedral units forming 1D chain structures in the lattice, due to the effect of stereochemically active lone pair 5s2 electrons in Sn2+. Such crystals have an SHG response of ≈1.4× Y‐cut α‐quartz for (S‐α‐PEA)SnBr3 and ≈0.9× Y‐cut α‐quartz for (S‐α‐PEA)SnCl3 at 1020 nm excitation, with high polarization ratio of SHG signals as well as wide bandgaps and transparency windows in the meanwhile. This work opens up a new platform for discovering more novel tin(II)‐based chiral perovskites with superior nonlinear optical properties in the future.
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Si, Wei-Dan, Kai Sheng, Chengkai Zhang, Zhi Wang, Shan-Shan Zhang, Jian-Min Dou, Lei Feng, Zhi-Yong Gao, Chen-Ho Tung y Di Sun. "Bicarbonate insertion triggered self-assembly of chiral octa-gold nanoclusters into helical superstructures in the crystalline state". Chemical Science, 2022. http://dx.doi.org/10.1039/d2sc03463h.

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A pair of unprecedented helical superstructures via self-assembly of inherently homochiral Au8 nanoclusters, [Au8(R/S-BINAP)3(o-HMBA)2]·2(HCO3), is obtained in the crystalline state, in which the HCO3− ions act as the bridge.
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Li, Tianyu, Luyao Ding, Yihong Kang, Xin-Qi Hao, Yujing Guo, Linlin Shi y Mao-Ping Song. "The synthesis, characterization and application of the binol-cages of R-/S-enantiomers". Chemical Synthesis 3, n.º 4 (31 de octubre de 2023). http://dx.doi.org/10.20517/cs.2023.39.

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In the past few years, significant efforts have been made to create and self-assemble covalent organic cages with increased complexity and functionality. However, although supramolecule cages have been widely recognized as probes to identify metal ions, the detection of mercury ions has not been fully developed. Here, we have designed and synthesized a pair of chiral cages with custom cavities based on the unique rigid structure of 1, 10-binaphthol (binol). Meanwhile, the supramolecular cage has excellent performance in high sensitivity and selectivity for detecting mercury ions. The UV titration results indicate that the binding ratio of the host to guest is 1:5. The titration curve conforms to the nonlinear fitting of the Hill function, which can obtain the binding constant K = 2.57 × 105 M-1 . Furthermore, the detection limit of 1.9 × 10-7 M can be obtained because the absorbance of cages exhibits a strong linear relationship with Hg2+ concentrations. This work provides a new method for selective recognition of ions by supramolecular cages.
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Tesis sobre el tema "Chiral ions pair"

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Saidah, Milane. "Synthèse énantiosélective de gamma-lactames possédant un centre tétrasubstitué". Electronic Thesis or Diss., Aix-Marseille, 2023. http://www.theses.fr/2023AIXM0034.

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Face à l'émergence des organocatalyseurs comme outils puissants de la catalyse énantiosélective, le développement de procédés impliquant des paires d'ions chirales a fait ses preuves. Notamment, la catalyse énantiosélective dirigée par un contre-ion (ACDC) représente une stratégie efficace pour les réactions énantiosélectives impliquant des espèces cationiques pro-chirales et des contre-anions énantiomériquement purs. Plus spécifiquement, les N-acyliminium cycliques sont des intermédiaires clés dans la préparation de gamma-lactames énantioenrichies. Sur la base du concept de l’ACDC, ce travail a été axé sur la construction de centres carbonés tétrasubstitués via une réaction d’alpha-amidoalkylation organocatalysée par des acides phosphoriques chiraux à partir de gamma-hydroxylactames
In view of the emergence of organocatalysts compounds as powerful tools for asymmetric catalysis, the development of processes involving chiral ion pairs has proven successful. Notably, Asymmetric Counterion-Directed Catalysis (ACDC) is well-known to be an efficient strategy for enantioselective reactions involving cationic species and enantiomerically pure counteranions. More specifically, cyclic N-acyliminium ions are key intermediates in the preparation of enantioenriched gamma-lactams. Based on the concept of ACDC, this work has focused on the construction of tetrasubstituted carbon centers via an organocatalyzed alpha-amidoalkylation reaction by chiral phosphoric acids from gamma-hydroxylactams
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2

Claraz, Aurélie. "Nouvelles applications de paires d’ions coopératifs chirales en organocatalyse : réactions énantiosélectives de protonation, de déprotonation et d’aldolisation directes vinylogues". Thesis, Rouen, INSA, 2012. http://www.theses.fr/2012ISAM0015.

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Le développement de nouvelles méthodologies énantiosélectives organocatalysées est au centre des projets de cette thèse. Nous avons plus particulièrement considéré le potentiel de "paires d'ions coopératifs" chirales possédant une partie ammonium dérivée des alcaloïdes de quinquina et une partie anionique à caractère nucléophile permettant d'activer un réactif. Dans un premier temps, nous avons employé un amidure d'ammonium chiral (généré in situ par réaction entre un amide N-silylé et un phénolate de quininium) comme base de Brønsted délivrée en quantité catalytiques en deux réactions distinctes. Initialement, cette stratégie nous a permis de mettre au point un procédé de désymétrisation de cétones prochirales par déprotonation éniantosélective. Bien que les excès énantiométriques obtenus restent modestes, notre approche constitue la première version organocatalysée. Puis, nous avons pu développer avec succès une nouvelle réaction d'aldolisation directe vinylogue énantiosélective de (5H)-furan-2-ones avec de bons rendements et diastérosélectivités anti et des excès énantiométriques allant jusqu'à 94 %. Dans un second temps, nous avons décrit deux nouveaux cycles catalytiques de protonation énantiosélective d'énolates masqués. Tout d'abord, l'utilisation d'hydrogénocarbonate de potassium et d'une amine chirale a conduit à l'obtention de cétones énantioenrichies α-substituées avec des excès énantiométriques allant jusqu'à 93 % à partir des trifluoacétates d'énols correspondants. Puis, les propriétés de base de Lewis de nos phénolates d'ammoniums quaternaires chiraux ont été valorisés lors de la protonation énantiosélectives d'éthers d'énols silylés en présence de phénols
This work deals with the development of new asymetric organocatalyzed methodologies. More particularly we were focused on using "cooperative chiral ion pairs" having an ammonium moiety derived from cinchona alkaloids and an anionic moiety with nucleophilic properties able to activate a reagent.Firstly, we used an in situ generated chiral ammonium amide (from the combination of an aminosilane and a quininium aryloxide) as a Brønsted base in two distinct reactions. Initially, this strategy was applied to an organocatalyzed desymmetrization of prochiral ketones by enantioselective deprotonation. Despite modest enantiometric excesses, this report constitutes the first example of an enantioselective orgonacatalyc approach. Then, an anti-selective direct vinylogous asymmetric aldol reaction of (5H)-furan-2-ones was achieved in good yields and enantioselectivities up to 94%.Secondly, we described two new catalytic cycles for the enantioselective protonation of latent enolates. By means of cinchona alkaloids and hydrogenocarbonates, enantioenriched α-substituted ketones were obtained with good enantiometric excesses up to 93% starting from the corresponding enol trifluoacetates. Finally, the nucleophilic properties of our ammonium phenoxide catalysts prompted us to develop an enantioselective protonation reaction of silyl enol ethers in the presence of phenol as achiral proton source
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Patwardhan, Neeraj Narendra. "Study of Synthesis, Reactions and Enantiomerization of Cα-Chiral Grignard Reagents". Diss., Virginia Tech, 2012. http://hdl.handle.net/10919/37814.

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The development of chiral organometallics for asymmetric synthesis is a topic of significant research in the recent past. The most studied in this class are the chiral organolithium reagents with many reported examples. The primary focus of our research is the development of Cα-chiral Grignard reagents, where the metal bearing α-carbon is the sole source of chirality. Examples of such Grignard reagents are rare owing to the problems associated with their synthesis, and their low configurational stability. We have studied these problems in three different modules of this project. Reactions of 1-magnesio-2,2-diphenyl-cyclopropylcarbonitrile with carbon electrophiles are first attempted in order to expand the utility of this configurationally stable Cα-chiral Grignard reagent in asymmetric synthesis. This reagent has been shown to be non-reactive towards carbon electrophiles at low temperatures. Consequently, we attempt to enhance the reactivity of this compound through two different approaches, Lewis-base activation and the "ate-complex" generation. The Magnesium/Halogen (Mg/X) exchange reactions have been shown to be extremely useful in the synthesis of complex Aryl, alkenyl (sp²) and alkynyl (sp) Grignard reagents. Examples of Mg/X exchange reactions of Alkyl (sp³) halides are, however, rare. Even more rare are such examples with secondary and tertiary alkyl halides, justifying the relative paucity of chiral Grignard reagents. In this module of our project, we study the Mg/X exchange reactions on secondary alkyl halides possessing a γ-hydroxyl group, as an internal activator for such Mg/X exchange reactions. Enantiomerization pathways of chiral organolithium compounds have been widely studied. However, few such studies have been performed on chiral Grignard reagents. In this module of the project, we studied the solvent assisted enantiomerization mechanism of the Cα-chiral 1-magnesio-2,2-diphenyl-cyclopropylcarbonitrile. Rate constant for the enantiomerization of this compound was measured in three different ethereal solvents to study the effect of solvent on the configurational stability. Finally, the order of the enantiomerization process with respect to [Et₂O] was studied in order to predict the mechanism of this process in Et₂O solvent. Our kinetic studies on the enantiomerization process provided us with a definitive picture for the enantiomerization of the Cα-chiral 1-magnesio-2,2-diphenyl-cyclopropylcarbonitrile, where solvation of the Grignard reagent preceded an ion-pair separation step which eventually lead to enantiomerization of the Grignard species. However, the precise structure of all the involved solvated intermediates could not be determined as kinetics was not able to distinguish between these intermediates. We next performed computational calculations to study the effect of solvation on the analogous 1-magnesio-cyclopropylcarbonitrile in order to address the unanswered questions from our kinetic studies.
Ph. D.
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Legros, Fabien. "Nouvelles applications de paires d'ions coopératifs chirales en organocatalyse : utilisations dans des réactions mettant en jeu l'acide de Meldrum et ses dérivés". Thesis, Normandie, 2017. http://www.theses.fr/2017NORMR026/document.

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Les travaux présentés dans ce manuscrit de thèse concernent la mise au point de nouvelles méthodologies de synthèse asymétrique en organocatalyse promues par des phénolates d’ammoniums quaternaires, catalyseurs de type paires d’ions coopératifs chirales, et des dérivés de l’acide de Meldrum comme substrats. Dans un premier temps, nous avons utilisé l’acide de Meldrum comme un précurseur de cétène via une cycloréversion induite par O-silylation grâce à une probase silylée, afin de réaliser une réaction de cycloaddition [2+2] avec un aldéhyde ou une imine catalysée par un phénolate d’ammonium chiral, permettant de former des β-lactones et des β-lactames. Les travaux effectués n’ont cependant pas permis d’obtenir le produit désiré. Dans un secont temps, nous avons exploité le caractère électrophile des dérivés disubstitués de l’acide de Meldrum et leur capacité à fragmenter suite à l’addition nucléophile d’un phénolate. Une première partie a été consacrée au développement d’une réaction monotope de désymétrisation de l’acide de Meldrum pour former des malonates dissymétriques après une étape d’alkylation in situ du carboxylate intermédiaire. Bien que de bons rendements isolés aient été obtenus, un maximum de 21% ee a pu seulement être atteint. Dans une seconde partie, nous avons mis au point une séquence originale, catalysée par un phénolate d’ammonium quaternaire chiral, qui est constituée (1) d’une addition nucléophile de phénolate suivie (2) d’une fragmentation avec perte d’acétone qui permet, après (3) une étape de décarboxylation de générer un acétal de cétène acyclique qui va subir (4) une réaction de protonation énantiosélective. Cette méthode a pu être appliquée à un large panel de substrats avec de bons rendements et des excès énantiomériques allant jusqu’à 70% ee
The work developed in this PhD thesis deals with the development of new asymmetric organocatalytic methodologies implying cooperative chiral ion pairing catalysis, by using chiral ammonium phenoxides as catalysts and Meldrum’s acid derivatives as substrates. First, we used the ability of Meldrum’s acid to generate acylketenes after cycloversion triggered by O-silylation thanks to a silylated probase in the presence of a chiral ammonium phenoxide. Such an approach was applied to the synthesis of β-lactones and β-lactames following a [2+2] cycloaddition reaction with aldehydes or imines respectively. Unfortunately, the desired products have never been observed. Then, we focused on disubstitued derivatives of Meldrum’s acids and their propensity to fragment after a nucleophilic addition of phenoxide. In a first part, we have developed a one-pot desymmetrization reaction of Meldrum’s acid derivatives to form dissymmetric malonates after an in-situ alkylation of the transient carboxylate. However, despite high isolated yields, only an unsatisfactory 21% ee could be reached. In a second part, we have developed an unprecedented sequence consisting of (1) a nucleophilic addition of phenol derivatives to Meldrum’s acid followed by (2) a fragmentation with loss of acetone, leading after (3) decaboxylation to the formation of an acyclic ketene acetal which is involved in (4) an enantioselective protonation reaction to provide a wide range of enantioenriched phenolic esters with moderate to excellent yield and up to 70% ee
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上木, 佑介 y Yusuke UEKI. "Development of Ion-Pair Cooperative Asymmetric Catalyses of Chiral Tetraaminophosphonium Salts Possessing Organic Anions". Thesis, 2012. http://hdl.handle.net/2237/16460.

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Shie, Ying-ying y 謝瑩瑩. "Enantioseparation of Acids by Partial Filling Technique of Capillary Electrophoretic Chromatography with π-Acid Derived Quinidine as Chiral Ion-Pair Reagent". Thesis, 2004. http://ndltd.ncl.edu.tw/handle/01261368607598987489.

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碩士
朝陽科技大學
應用化學系碩士班
92
The potential of 3,5-dinitrobenzoyl quinidine as chiral selector added to a non-aqueous background buffer for the capillary electrophoretic separation of the enantiomers of N-derivatized amino acids and non-steroidal anti-inflammatory drugs are evaluated. Separation is based on chiral analytes of R or S of negatively charged and positively charged quinidine-derived chiral selector to form temporary ion-pair, because of different molecular interactions and mobiling. As a result, the differences in the overall migration of analytes can be achievd. To suppress one problems associated with the high UV absorption of the chiral selector and thus the high detecting background in the ‘total filling technique’, the ‘partial filling technique’ has been adopted. Several parameters including selector filling time and length of selector zone, selector concentration, type of non-aqueous background electrolyte and length of column have been evaluated. Optimun experimental conditions were found with a electrolyte made of 80 mM acetic acid, 20 mM triethylamine and 150 mM 3,5-dinitrobenzoyl quinidine in an EtOH-MeOH (60:40, v/v), and at voltage of –30kV. Under these conditions, (R) and (S) enantiomers of 3,5-dinitrobenzoyl leucine could be separated with α=1.10, Rs=5.16. (R) and (S) enantiomers of ketoprofen could be separated with α=1.06, Rs=1.13. Similar resolution, and efficiencies were observed for other analytes. 3,5-dinitrobenzoyl quinidine as chiral selector can be utilized to separate several kinds of compound induding aromatic π acid, aromatic π base and ascorbic acid.
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Capítulos de libros sobre el tema "Chiral ions pair"

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Buese, Mark A. y Thieo E. Hogen-Esch. "Stereoelective Anionic Polymerization of Chiral Vinyl Monomers Via Interconverting Ion Pair Epimers". En Recent Advances in Anionic Polymerization, 231–47. Dordrecht: Springer Netherlands, 1987. http://dx.doi.org/10.1007/978-94-009-3175-6_16.

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de Biasi, V., M. B. Evans y W. J. Lough. "A Note on Chiral Ion-Pair Chromatography of Novel Basic Antihypertensive Agents". En Recent Advances in Chiral Separations, 93–96. New York, NY: Springer US, 1991. http://dx.doi.org/10.1007/978-1-4684-8282-9_13.

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Rueping, M. y E. Sugiono. "New Developments in Enantioselective Brønsted Acid Catalysis: Chiral Ion Pair Catalysis and Beyond". En Ernst Schering Foundation Symposium Proceedings, 301–50. Berlin, Heidelberg: Springer Berlin Heidelberg, 2008. http://dx.doi.org/10.1007/2789_2008_085.

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Gaskell, R. M. y B. Crooks. "A Note on Analytical and Preparative Chiral Resolution of Some Aminoalcohols by Ion-Pair High-Performance Liquid Chromatography". En Chiral Separations, 65–70. Boston, MA: Springer US, 1988. http://dx.doi.org/10.1007/978-1-4615-6634-2_8.

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Ali, Imran y Hassan Y. Aboul-Enein. "Speciation of Metal Ions by Ion-Pair, Micellar Electrokinetic, Size Exclusion, Chiral, Capillary Electro-, and Supercritical Fluid Chromatographic Methods". En Instrumental Methods in Metal Ion Speciation, 243–61. CRC Press, 2006. http://dx.doi.org/10.1201/9781420019407-8.

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"Speciation of Metal Ions by Ion-Pair, Micellar Electrokinetic, Size Exclusion, Chiral, Capillary Electro-, and Supercritical Fluid Chromatographic Methods". En Instrumental Methods in Metal Ion Speciation, 243–61. CRC Press, 2006. http://dx.doi.org/10.1201/9781420019407.ch8.

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Heldin, E. "CHIRAL SEPARATIONS | Ion-Pair Chromatography". En Encyclopedia of Separation Science, 2358–69. Elsevier, 2000. http://dx.doi.org/10.1016/b0-12-226770-2/03151-3.

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