共查询到20条相似文献,搜索用时 15 毫秒
1.
Krupcík J Mydlová J Májek P Simon P Armstrong DW 《Journal of chromatography. A》2008,1186(1-2):144-160
In this paper, methods are described that are used for studying first-order reaction kinetics by gas chromatography. Basic theory is summarized and illustrated using the interconversion of 1-chloro-2,2-dimethylaziridine enantiomers as a representative example. For the determination of the kinetic and thermodynamic activation data of interconversion the following methods are reviewed: (i) classical kinetic methods where samples of batch-wise kinetic studies are analyzed by enantioselective gas chromatography, (ii) stopped-flow methods performed on one chiral column, (iii) stopped-flow methods performed on an achiral column or empty capillary coupled in series with two chiral columns, (iv) on-flow method performed on an achiral column coupled in series with two chiral columns, and (v) reaction gas chromatography, known as a dynamic gas chromatography, where the interconversion is performed on chiral column during the separation process. The determination of kinetic and thermodynamic activation data by methods (i) through (iv) is straightforward as the experimental data needed for the evaluation (particularly the concentration of reaction constituents) are accessible from the chromatograms. The evaluation of experiments from reaction chromatography method (v) is complex as the concentration bands of reaction constituents are overlapped. The following procedures have been developed to determination peak areas of reaction constituents in such complex chromatograms: (i) methods based on computer-assisted simulations of chromatograms where the kinetic activation parameters for the interconversion of enantiomers are obtained by iterative comparison of experimental and simulated chromatograms, (ii) stochastic methods based on the simulation of Gaussian distribution functions and using a time-dependent probability density function, (iii) approximation function and unified equation, (iv) computer-assisted peak deconvolution methods. Evaluation of the experimental data permits the calculation of apparent rate constants for both the interconversion of the first eluted (k (A-->B)(app)) as well as the second eluted (k(B-->A)(app)) enantiomer. The mean value for all the rate constants (from all the reviewed methods) was found for 1-chloro-2,2-dimethylaziridine A-->B enantiomer interconversion at 100 degrees C: k (A-->B)(app)=21.2 x 10(-4)s(-1) with a standard deviation sigma=10.7 x 10(-4). Evaluating data for reaction chromatography at 100 degrees C {k (app)=k(A-->B)(app)=k(B-->A)(app)=13.9 x 10(-4)s(-1), sigma=3.0 x 10(-4)s(-1)} shows that differences between k(A-->B)(app) and k(B-->A)(app) are the same within experimental error. It was shown both theoretically and experimentally that the Arrhenius activation energy (E(a)) calculated from Arrhenius plots (lnk(app) versus 1/T) is proportional to the enthalpy of activation {E(a)=DeltaH+RT}. Statistical treatment of Gibbs activation energy values gave: DeltaG (app)=110.5kJmol(-1), sigma=2.4kJmol(-1), DeltaG (A-->B)(app)=110.5kJmol(-1), sigma=2.2kJmol(-1), DeltaG (B-->A)(app)=110.3kJmol(-1), sigma=2.8kJmol(-1). This shows that the apparent Gibbs energy barriers for the interconversion of 1-chloro-2,2-dimethylaziridine enantiomers are equal DeltaG (app)=DeltaG(A-->B)(app)=DeltaG(B-->A)(app) and within the given precision of measurement independent of the experimental method used. 相似文献
2.
Májek P Mydlová J Krupcík J Lehotay J Armstrong DW Cotton FA 《Journal of separation science》2006,29(15):2357-2364
A classical kinetic method was used to determine the energy barrier for the inter-conversion of 2,3-pentadienedioic acid enantiomers. Each individual enantiomer was isolated by collecting the appropriate peaks from the HPLC enantiomeric separation, of racemic 2,3-pentadienedioic acid. The isolated enantiomers were racemized at 22 degrees C using various interconversion times. The ratio of enantiomers in each reaction solution was determined by HPLC at 22 degrees C. The corresponding peak areas of the enantiomers and the interconversion times obtained from the HPLC chromatograms were used to calculate both the interconversion rate constants describing (+)--> (-) and (-) --> (+) interconversions as well as the energy barriers. It was confirmed that the interconversion of 2,3-pentadienedioic acid enantiomers is a firstorder kinetic reaction. Both semiempirical and ab initio methods were used to explore the mechanism of the interconversion of 2,3-pentadienedioic acid enantiomers, and to calculate the interconversion energy barrier. Comparison of the interconversion energy barriers found by the ab initio method (deltaG# = 110.7 kJ/mol) and by classical kinetics in the mobile phase solution at 22 degrees C (delta Gapp = 93.9+/-0.2 kJ/mol) shows a difference which may be attributed to the different conditions assumed in the theoretical calculation (i.e., a gaseous state) and the actual experimental conditions (i. e., liquid solution) and a possible catalytic effect of the solution composition. 相似文献
3.
Mydlová J Krupcík J Májek P Skacáni I Jakubík T Sandra P Armstrong DW 《Journal of chromatography. A》2007,1150(1-2):124-130
The enantiomers of dialkyl 2,3-pentadienedioate undergo interconversion during gas chromatographic separation on chiral stationary phases. In this paper the on-column apparent interconversion kinetic and thermodynamic activation data were determined for dimethyl, diethyl, propylbutyl and dibutyl 2,3-pentadienedioate enantiomers by gas chromatographic separation of the racemic mixtures on a capillary column containing a polydimethylsiloxane stationary phase coupled to 2,3-di-O-methyl-6-O-tertbutyldimethylsilyl-beta-cyclodextrin. A deconvolution method was used to determine the individual enantiomer peak areas and retention times that are needed to calculate the interconversion rate constants and the energy barriers. The apparent rate constants and interconversion energy barriers decrease slightly with an increase in the alkyl chain length of the dialkyl 2,3-pentadienedioate esters. The optimum conformation of the dialkyl 2,3-pentadienedioate molecules, their separation selectivity factors and apparent interconversion enthalpy and entropy data changes with the alkyl chain length. The dependence of the apparent interconversion energy barrier (deltaG(app)(a-->b), deltaG(app)(b-->a)) on temperature was used to determine the apparent activation enthalpy (deltaH(app)(a-->b), deltaH(app)(b-->a)) and apparent entropy (deltaS(app)(a-->b), deltaS(app)(a-->b)) (where a denotes the first and b second eluted enantiomer). The comparison of the activation enthalpy and entropy (deltaS(app)(a-->b), deltaS(app)(a-->b)) indicated that the interconversion of dialkyl 2,3-pentadienedioate enantiomers on the HP-5+Chiraldex B-DM column series is an entropy driven process at 160 degrees C. Data obtained for dimethyl 2,3-pentadienedioate enantiomers on the HP-5+Chiraldex B-DM column series at 120 degrees C (deltaG(app)(a-->b) = 123.3 and deltaG(app)(b-->a) = 124.4 kJ mol(-1)) corresponds (at the 95% confidence interval) with the value of deltaG(#) = 128+/-1 kJ mol(-1) found at this temperature by gas chromatography using a two-dimensional stop flow technique on an empty capillary column [V. Schurig, F. Keller, S. Reich, M. Fluck, Tetrahedron: Asymmetry 8 (1997) 3475]. 相似文献
4.
Mydlová J Benická E Krupcík J Sandra P Armstrong DW 《Journal of chromatographic science》2004,42(10):516-523
A novel on-flow gas chromatographic (GC) method is developed for the determination of the kinetic rate constants and interconversion energy barrier of thermally labile enantiomers. The validity of the developed method is approved by the study of interconversion of 1-chloro-2,2-dimethylaziridine enantiomers on an achiral column. The overall experiments are performed in a series of three columns placed in two independently heated GC ovens. The racemate of the 1-chloro-2,2-dimethylaziridine is injected and separated in the first chiral column at 60 degrees C in which the interconversion of enantiomers is suppressed. Separated enantiomers are then transferred into the achiral column, where the enantiomers are interconverted at a selected temperature under the current carrier gas flow. Effluent from this column is transferred into the second chiral column, where the native enantiomers and those originated by the on-flow interconversion on an achiral column are again separated at 60 degrees C. Chromatograms obtained by monitoring the effluents from the second chiral column are used to determine the peak areas of the original and the newly interconverted enantiomers. The corresponding peak areas and the interconversion times are used to calculate the interconversion rate constants and energy barriers of the 1-chloro-2,2-dimethylaziridine enantiomers. The apparent energy barriers of the enantiomers of 1-chloro-2,2-dimethylaziridine are equal for both enantiomers within a 95% confidence interval and independent of the polarity of the stationary phase of the column in which the interconversion of enantiomers occur. 相似文献
5.
Mydlová J Krupcík J Májek P Skacáni I Jakubík T Armstrong DW 《Journal of separation science》2006,29(10):1497-1507
The enantiomers of dimethyl-2,3-pentadienedioate undergo interconversion during gas chromatographic separation on 2,6-di-O-methyl-3-O-pentyl-beta-, 2,6-di-O-methyl-3-O-pentyl-gamma-, and 2,3-di-O-methyl-6-O-tert butyldimethylsilyl-beta-CD chiral stationary phases. The combination of a deconvolution method with an internal standard was used to determine individual enantiomer peak areas and retention times needed for the calculation of the interconversion rate constants and the energy barrier for dimethyl-2,3-pentadienedioate enantiomers. The kinetic and thermodynamic data obtained for the interconversion data (rate constants, energy barriers, enthalpies, and entropies) were in good agreement with the published data (Trapp, O., Schurig, V., Chirality 2002, 14, 465-470) using permethylated-beta-CD (Chirasil-beta-Dex). 相似文献
6.
When enantiomers separated by chromatography or capillary electrophoresis undergo interconversion reaction (enantiomerization) during the separation, it leads to a typical detection pattern: two individual peaks of the separated enantiomers are connected with a plateau consisting of a mixture of both separated enantiomers. We propose a separation method for determination of all individual rate constants (or inversion barriers) of the interconversion. The method enables to distinguish which part of interconversion takes place in the free (unbound) form of the analyte and which part in the complexed (bound) form. Further, we propose a complete dynamic model of capillary electrophoresis of interconverting enantiomers based on solving a complete set of continuity equations for all constituents of the separation system together with complexation and acid-base equilibria. This allows a simulation of both linear and nonlinear mode of separation and understanding all processes taking place in such enantioseparation systems. We demonstrate the applicability of the method on determination of the rate constants of interconversion of oxazepam enantiomers separated in systems with charged cyclodextrin chiral selectors. 相似文献
7.
The interconversion of cis and trans isomers of dipeptides containing C-terminal proline was studied by dynamic chromatography on zwitterionic chiral stationary phases at temperatures ranging from −15 °C to +45 °C The cis–trans isomers could be separated below 0 °C and above 0–10 °C plateau formation and peak coalescence phenomena occurred, which is characteristic for a dynamic process at the time-scale of partitioning. At and above room temperature, full coalescence was observed, which allowed separations of enantiomers without interference from interconversion effects. Analysis of the dynamic elution profiles of the interconverting peptides allowed the determination of isomerization rate constants and thermodynamic activation parameters (isomerization enthalpy, entropy and activation energy). In accordance with established results, isomerization rates and thermodynamic parameters were found to depend on the nature of the N-terminal amino acid. Isomerization barriers were only slightly lower than values determined with other methods but significant differences in the relative contributions of the activation enthalpy and entropy as well as isomerization rates pointed toward selector-moderated isomerization dynamics. 相似文献
8.
Enantioselective chromatographic methods, representing the most commonly used techniques for the determination of enantiomeric ratios, can also be used for the evaluation of stereochemical integrity. In the present study, dynamic capillary electrokinetic chromatography (DEKC) was employed to determine the enantiomerization barrier of thalidomide. In the presence of the chiral mobile phase additive carboxymethyl-beta-cyclodextrin, the interconverting enantiomers of thalidomide produced characteristic elution profiles exhibiting plateaus and/or peak broadening between 25 and 55 degrees C at pH 8. To obtain the enantiomerization barrier of thalidomide from experimental data, the fast and efficient simulation program ChromWin was used to simulate the experimental interconversion profiles and to obtain the apparent rate constants k1app(T). Additionally, these values were compared with the novel approximation function for the direct calculation of enantiomerization barriers from chromatographic parameters of elution profiles. From the rate constants k1app(T) of temperature-dependent measurements the kinetic activation parameters deltaG(T)#,deltaH#, and deltaS# of the enantiomerization of thalidomide were obtained. At 25 degrees C, the enantiomerization barrier deltaG# was determined to be 102 +/- 1 kJ/mol at pH 8 in the dynamic electrokinetic chromatographic experiment. 相似文献
9.
The activation parameters for the interconversion of atropisomers (P- and M-enantiomer) of core-twisted perylene bisimides have been determined by dynamic NMR spectroscopy (DNMR) and time- and temperature-dependent CD spectroscopy. By comparing the activation parameters of a series of perylene bisimides containing halogen or aryloxy substituents in the bay area (1,6,7,12-positions), a clear structure-property relationship has been found that demonstrates that the kinetic and thermodynamic parameters for the inversion of enantiomers are dependent on the apparent overlap parameter Sigmar* of the bay substituents. This study reveals a high stability (DeltaG(368 K) = 118 kJ/mol) for the atropo-enantiomers of tetrabromo-substituted perylene bisimide in solution. Accordingly, the enantiomers of this derivative could be resolved by HPLC on a chiral column. These enantiomers do not racemize in solution at room temperature and, thus, represent the first examples of enantiomerically pure core-twisted perylene bisimides. 相似文献
10.
The rate constants and activation energy barriers DeltaG# of diastereomerization reaction of flavanones: naringin, narirutin, hesperidin and neohesperidin were determined. The stopped-flow HPLC (SFM-HPLC), dynamic HPLC (D-HPLC) and enantioselective HPLC combined with the classical kinetic method were applied for determination of these parameters. It was found that the rate constants of diastereomerization were about eight times higher for naringin and narirutin (1.9 x 10(-5) s(-1)) than for hesperidin and neohesperidin (2.4 x 10(-6) s(-1)). No significant differences in the rate of diastereomerization were found between neohesperidosides and corresponding rutinosides. 相似文献
11.
《Tetrahedron: Asymmetry》2004,15(6):925-933
The activation barriers for the interconversion between the enantiomers of 5,5-dimethyl-3-(o-aryl)-2,4-oxazolidinediones (M⇌P) have been determined by temperature dependent NMR and by enantioresolution on chiral sorbents via HPLC. The activation barriers were found to increase linearly with the size of the van der Waals radii of the ortho-halogen substituents. The enantiomers of the o-iodo derivative were micropreparatively enriched on a Chiralpak AD column, leading to the determination of its barrier to rotation via thermal racemization and resulting in the assignments of conformations in the presence of the optically active chiral auxiliary (S)-(+)-1-(9-anthryl)-2,2,2-trifluoro ethanol [(S)-TFAE]. 相似文献
12.
Mydlová J Fedurcová A Lehotay J Krupcík J Májek P Armstrong DW He BL Cotton FA 《Journal of separation science》2006,29(17):2594-2599
In this paper, an HPLC method is used to determine the enantiomerization barrier of 2,3-pentadienedioic acid enantiomers. The racemate of 2,3-pentadienedioic acid was separated by HPLC on a chiral CHIROBIOTIC T column with a 90:10 (100:0.5:0.5 MeOH/HOAc/TEA)/H2O mobile phase. Peak areas of enantiomers prior to (A(+)0, A(-)0) and after the separation (A(+), A(-)), were used for calculation of the rate constants and the enantiomerization barrier, as determined by computer-assisted peak deconvolution of the peak clusters on the chromatograms. The kinetic equation for irreversible reactions was used to determine the apparent enantiomerization rate constants and the interconversion energy barrier. The dependence of the apparent enantiomerization barrier (deltaG1(app), deltaG-1(app)) on temperature was used to determine the apparent activation enthalpy (deltaH1(app), deltaH(-1)app) and entropy (deltaS1(app), deltaS-1(app)) for the interconversion of 2,3-pentadienedioic acid enantiomers, where the coefficients 1 and -1 designate the interconversions (+) --> (-) and (-) --> (+), respectively. 相似文献
13.
Hinterwirth H Lämmerhofer M Preinerstorfer B Gargano A Reischl R Bicker W Trapp O Brecker L Lindner W 《Journal of separation science》2010,33(21):3273-3282
Phosphorylated carbohydrates are important intracellular metabolites and thus of prime interest in metabolomics research. Complications in their analysis arise from the existence of structural isomers that do have similar fragmentation patterns in MS/MS and are hard to resolve chromatographically. Herein, we present selective methods for the liquid chromatographic separation of sugar phosphates, such as hexose and pentose phosphates, 2‐ and 3‐phosphoglycerate, dihydroxyacetone phosphate and glyceraldehyde 3‐phosphate, as well as glucosamine 1‐ and 6‐phosphate utilizing mixed‐mode chromatography with reversed‐phase/weak anion‐exchangers and a charged aerosol detector. The best results were obtained when the reversed‐phase/weak anion‐exchanger column was operated under hydrophilic interaction liquid chromatography elution conditions. The effects of various chromatographic parameters were examined and are discussed on the basis of a simple stoichiometric displacement model for explaining ion‐exchange processes. Employed acidic conditions have led to the complete separation of α‐ and β‐anomers of glucose 6‐phosphate at low temperature. The anomers coeluted in a single peak at elevated temperatures (>40°C) (peak coalescence), while at intermediate temperatures on‐column interconversion with a plateau in‐between resolved anomer peaks was observed with apparent reaction rate constants between 0.1 and 27.8×10?4 s?1. Dynamic HPLC under specified conditions enabled to investigate mutarotation of phosphorylated carbohydrates, their interconversion kinetics, and energy barriers for interconversion. A complex mixture of six hexose phosphate structural isomers could be resolved almost completely. 相似文献
14.
Methods for the separation of photosensitizer isomers, such as benzoporphyrin derivative monoacid, benzoporphyrin ethyl monoacid, 2-[1-hexyloxyethyl]-2-devinylpyropheophorbide-a, diethyleneglycol diester benzoporphyrin derivative, tin ethyl etiopurpurin, and phthalocyanine tetrasulfonate, have been systematically developed by CE. Detection was accomplished by UV absorption at 214 nm or by LIF with excitation at 442/488 nm and emission at 690 nm. The effects of three major experimental parameters of buffer types, organic solvents, and surfactant additives are described. The optimized separation conditions were determined so as to provide satisfactory separation efficiency and analysis time. The methods are shown to be suitable for the separation and determination of porphyrin and phthalocyanines regioisomers, diastereoisomers, and enantiomers. 相似文献
15.
Chiral liquid chromatography contribution to the determination of the absolute configuration of enantiomers 总被引:2,自引:0,他引:2
Roussel C Del Rio A Pierrot-Sanders J Piras P Vanthuyne N 《Journal of chromatography. A》2004,1037(1-2):311-328
The review covers examples in which chiral HPLC, as a source of pure enantiomers, has been combined with classical methods (X-ray, vibrational circular dichroism (VCD), enzymatic resolutions, nuclear magnetic resonance (NMR) techniques, optical rotation, circular dichroism (CD)) for the on- or off-line determination of absolute configuration of enantiomers. Furthermore, it is outlined that chiral HPLC, which associates enantioseparation process and classical purification process, opens new perspectives in the classical determination of absolute configuration by chemical correlation or chemical interconversion methods. The review also contains a discussion about the various approaches to predict the absolute configuration from the retention behavior of the enantiomers on chiral stationary phases (CSPs). Some examples illustrate the advantages and limitations of molecular modeling methods and the use of chiral recognition models. The assumptions underlying some of these methods are critically analyzed and some possible emerging new strategies are outlined. 相似文献
16.
Enantioselective stopped-flow multidimensional gas chromatography (stopped-flow MDGC) is a fast and simple technique to determine enantiomerization (inversion) barriers in the gas phase in a range of delta G#gas(T)=70-200 kJ mol(-1). After complete gas-chromatographic separation of the enantiomers in the first column, gas phase enantiomerization of the heart-cut fraction of one single enantiomer is performed in the second (reactor) column at increased temperature and afterwards this fraction is separated into the enantiomers in the third column. From the observed de novo enantiomeric peak areas a(j), the enantiomerization time t and the enantiomerization temperature T, the enantiomerization (inversion) barrier delta G#gas(T) is determined and from temperature-dependent experiments, the activation enthalpy delta H#gas and the activation entropy delta S#gas are obtained. Enantiomerization studies on chiral 1-chloro-2,2-dimethylaziridine by stopped-flow MDGC yielded activation parameters of nitrogen inversion in the gas phase, i.e., delta G#gas(353 K)=110.5+/-0.5 kJ mol(-1), delta H#gas=71.0+/-3.8 kJ mol(-1) and delta S#gas=-109+/-11 J mol(-1) K(-1). By the complementary method of dynamic gas chromatography (GC), the apparent enantiomerization (inversion) barrier of 1-chloro-2,2-dimethylaziridine in the gas-liquid biphase system was found delta G#app(353 K)=108 kJ mol(-1). The values obtained by stopped-flow MDGC in the gas phase were used to calculate the activation parameters of nitrogen inversion of 1-chloro-2,2-dimethylaziridine in the liquid phase in the presence of the chiral selector Chirasil-nickel(II), i.e.. deltaG#liq(353 K)=106.0+/-0.4 kJ mol(-1), delta H#liq=68.3+/-1.4 kJ mol(-1) and deltaS#liq=-106+/-3.0 J mol(-1) K(-1). 相似文献
17.
《Journal of computational chemistry》2018,39(8):424-437
The focal‐point analysis (FPA) technique is used for the definitive characterization of conformational interconversion parameters, including activation energy barriers, activation free energies, and kinetic rate coefficients at 298 K, of two n‐alkanes, n‐butane, and n‐pentane, yielding the first complete analysis of their interconversion kinetics. The FPA implementation developed in this study is based on geometry optimizations and harmonic frequency computations carried out with density functional theory methods and single‐point energy computations up to the CCSD(T) level of electronic structure theory using atom‐centered Gaussian basis sets as large as cc‐pV5Z. The anharmonic vibrational computations are carried out, at the MP2/6‐31G* level of theory. Reflecting the convergence behavior of the Gibbs free‐energy terms and the interconversion parameters, well‐defined uncertainties, mostly neglected in previous theoretical studies, are provided. Finally, the effect of these uncertainties on the concentrations of the conformers of n‐butane and n‐pentane is examined via a global Monte–Carlo uncertainty analysis. © 2017 Wiley Periodicals, Inc. 相似文献
18.
《Tetrahedron: Asymmetry》2006,17(22):3158-3162
The synthesis and enantioseparation of chiral 3,4-dihydro-1,2,4-benzothiadiazine 1,1-dioxide derivatives are reported herein. A HPLC stopped-flow procedure was applied to the determination of rate constants and free energy barriers of enantiomerization of the compounds synthesized in the presence of achiral stationary phase. The individual enantiomers of the studied compounds were isolated in parallel by preparative HPLC on a Chiraspher NT column. Rate constants and free energy barriers of enantiomerization were determined in the mobile phase. The results were used to determine the influence of the chiral stationary phase on the enantiomerization process. 相似文献
19.
The orthogonal syn and anti isomers, originated by the restricted rotation about the Ar-C(O)Bu(t) single bonds in 1,4-bis(2,2-dimethylpropanoyl)durene (2e), have been separated by preparative thin layer chromatography. In solution they reach an equilibrium where the syn-anti ratio depends upon the polarity of the solvent. This allowed us to assign the anti structure, which has a null dipole moment, to the least retained isomer. The free energy of activation (DeltaG) for the interconversion was found to be 22.5 kcal mol(-)(1), a value high enough for identifying these species as configurational isomers. When less hindered derivatives, also having two RCO (R = Pr(i), Et, Me) substituents in the positions 1,4 of the durene moiety, were examined, the syn and anti forms could be detected only at low temperature by means of NMR spectroscopy. The corresponding interconversion barriers (DeltaG = 13.4, 11.7, 10.9 kcal mol(-)(1), respectively) are, in fact, much lower than for R = Bu(t), indicating that in these cases we are dealing with conformational rather than with configurational isomers. 相似文献
20.
Verbeck GF Gillig KJ Russell DH 《European journal of mass spectrometry (Chichester, England)》2003,9(6):579-587
Preliminary results from a liquid nitrogen-cooled ion mobility (IM) orthogonal-time-of-flight (o-ToF) mass spectrometer applied to the separation of electronic isomers of Kr2+ and methanol radical cations (conventional and distonic) are presented. Ab initio calculations were used to estimate the energies and energy barriers to interconversion between conventional (CH3OH*+) and distonic (CH2*OH2+) radical cations. In addition, computations and experiments are used to compare ion-neutral collision cross-sections for CH3OH*+ and CH2*OH2+ radical cations and suggest that the mobility separation is achieved by ion-neutral interactions between ions and neutral buffer gas. 相似文献