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1.
A laboratory working procedure is described for silanization of glass capillaries with bis(cyanopropyl)tetramethyldisiloxane, prior to coating with XE-60-L -valine-(S)-α-phenylethylamide as chiral stationary phase. GC columns thus prepared exhibit good inertness and no long-term deterioriation of enantioselectivity up to 220°C. A general procedure is given for derivatization of simple and of polyfunctional amino acids, in a batch mixture, simultaneously, and completely at both the N- and the C-terminus and all other protic functions. Within the seven series of N-pivaloyl amino acid esters tested (methyl to neopentyl), baseline separation is obtained for all R/S pairs, including the proline derivative. 相似文献
2.
Six chiral diamide stationary phases (CSPs), namely N-(3-carbobenzoxypropionyl)-L-Val-tert-butylamide (CSP-1), N-undecenoyl-L-Val-S-α-phenylethylamide (CSP-2), N-undecenoyl-L-Val-R-α-phenylethylamide (CSP-3), OV-225-L-Val-tert-butylamide (CSP-4), XE-60-L-Val-tert-butylamide (CSP-5) and polycyanoethyl vinyl siloxane-L-Val-tert-butylamide (CSP-6), were inves-tigated and CSP-6 was crosslinked within narrow bore (70 μm) fused silica capillary columns. Theseparation of amino acid enantiomers on this narrow bore column by gas chromatography (GC) isillustrated. 相似文献
3.
Iwao Abe Kennji Terada Taketoshi Nakahara Hartmut Frank 《Journal of separation science》1998,21(11):592-596
New chiral polysiloxanes have been prepared as stationary phases for gas chromatography, with (S)-(–)-t-leucine-t-butylamide, (S)-(–)-t-leucine-(S)-(–)-1-phenylethylamide, (S)-(–)-t-leucine-(S)-(–)-1-(α-naphthyl)ethylamide, (S)-(–)-t-leucine-(R)-( + )-1-phenylethylamide, and (S)-(–)-t-leucine-(R)-( + )-1-(α-naphthyl)ethylamide as selectors. Immobilization is achieved by radical-induced cross-linking with 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (V4) and dicumyl peroxide (DCUP) as cross-linking reagents and cured at 170°C. Under these conditions, racemization of (S)-(–)-t-leucine is less than 4.5% (R) for 1 h curing, while for polysiloxanes with the conventional (S)-(–)-valine selectors about 20% of R-enantiomers are formed by racemization. In the presence of 5% (w/w) V4 and 6% of DCUP with regard to the phases, 70–80% immobilization is achieved; without V4, the degree of immobilization is about 50% for both the (S)-(–)-t-leucine and (S)-(–)-valine selectors. As the size of the amide moieties of the selectors increases from t-butyl to 1-(α-naphthyl)ethyl, the degree of immobilization decreases. If the curing time is prolonged to 2 h, the extent of racemization increases. The selectivity factors achieved for amino acid enantiomers and similar pharmaceuticals are generally higher than those obtained with the corresponding non-immobilized Chirasil-Val phases. 相似文献
4.
Jaiver Osorio Grisales Pablo J. LebedSonia Keunchkarian Francisco R. GonzálezCecilia B. Castells 《Journal of chromatography. A》2009,1216(40):6844-6851
This paper reports the study of poly(oxyethylene) as a solvent for heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin (PM-β-CD) and the potential of these mixtures for constructing enantioselective gas chromatography columns. Enantioseparations of volatile racemic mixtures using capillaries coated with 10–50% PM-β-CD diluted in Carbowax 20M were evaluated. The influence of the polymer type on retention, separation and reproducibility over a period of time is critically discussed. The poly(oxyethylene)-based columns were also compared to columns prepared by dilution of PM-β-CD in two polysiloxanes, SE-30 and SE-54, at several temperatures. Finally, we evaluated a new stationary phase prepared by crosslinking the chiral selector to the poly(oxyethylene) matrix. 相似文献
5.
New chiral polymers have been prepared by conversion of cyano groups of polysiloxanes XE-60 and OV-225 into carboxylic groups and subsequent coupling to give the respective S-valine-R-α-phenyl-ethyl amide. In contrast to the corresponding stationary phases with S-α-phenylethyl amide groups, which have been used for the resoultion of trifluoroacetylated hexose derivatives, the new phase show high enantioselectivity for pentose and 6-deoxyhexose derivatives. 相似文献
6.
Ladislav Sojk 《Journal of chromatography. A》1980,190(2)
The optimal separation properties of Carbowax 20M as a stationary phase in 300-m glass capillary columns at temeperatures below its lower temperature limit (60°) in terms of the selectivity, efficiency and speed of the gas chromatographic analysis of isomeric C10---13n-alkenes were investigated.In the separation of isomeric n-alkenes two possible states of the Carbowax stationary phase below 60° were used (solid state and intermediate liquid state), and the dependence of the retention of the isomers on temperature was studied. The region of the hysteresis portion of the ICW = f(T)diagram permits the continuous setting of column selectivity. The efficiency of the column at temperatures below the lower temperature limit of Carbowax 20M depends on the spatial cis-trans configuration of n-alkenes and, in the solid state, for cis-isomers is comparable to the high efficiency of this column at higher temperatures (115°). Utilization of Carbowax 20M in the solid state made it possible to achieve faster and more complete separations of the eleven possible positional and spatial isomers of n-tridecenes in comparison with previous methods. 相似文献
7.
Gas-liquid chromatography of thioesters of perfluorocarboxylic acids 1. Characteristics of retention
Retention of thioesters of perfluoropentanoic acid C4F9C(O)SR was studied by GLC on packed and capillary columns using stationary phases SE-30, SKTFT-50X, XE-60, and Carbowax 20M.
The retention indices of these compounds were calculated, and their relationship with the structure of the compounds and the
conditions of the analysis were established.
Translated fromIzvestiya Akademii, Nauk. Seriya Khimicheskaya, No. 5, pp. 984–986, May, 1997. 相似文献
8.
Jerald S. Bradshaw Patricia K. Thompson Reed M. Izatt Frederick G. Morin David M. Grant 《Journal of heterocyclic chemistry》1984,21(3):897-901
A series of chiral diphenyl-substituted macrocyclic polyether-diester ligands have been prepared from the chiral diphenyl-substituted tetraethylene glycol. Enantiomeric recogntion by the chiral diphenyl-substituted pyridino-diester-18-crown-6 compound ( 7 ) was studied by temperature dependent 1H NMR spectroscopy in deuteriodichloromethane. This ligand exhibited chiral recognition when complexed with the hydrogen per-chlorate salts of (R)- and (S)-α-(1-naphthyl)ethylamine and (R)- and (S)-methyl phenylalaninate. 相似文献
9.
M. D. Ossowska-Chruściel 《Liquid crystals》2013,40(8):1159-1165
A secondary chiral (R)-(?)-2-alcohol underwent the Mitsunobu reaction with triphenylphosphine, diethyl azodicarboxylate and ethyl 4-hydroxybiphenylcarboxylate, resulting in the desired (S)-(+)-product with high enantiomeric purity (>99% ee), with the chiral branched chain attached to the biphenyl. This method is operationally simple and provides the very important chiral precursor in good yields (62% in dry THF and 72% in dry Et2O). The condensation of the (S)-(+)-acid chloride from this material and a suitable 4-n-alkylthiophenol in toluene in the presence of pyridine or triethylamine furnishes the chiral (S)-(+)-thiobenzoate liquid crystals in good yields (80–83% in pyridine and 65–68% in Et3N). (S)-(+)-4-(1-Methylheptyloxy)biphenyl 4-alkylthiobenzoates are abbreviated (S)-MHOBSn , where n varies from 4 to 10 and denotes the number of carbon atoms in the alkyl chain. DSC, polarizing microscopy and X-ray diffraction showed that the (S)-MHOBSn series possesses a rich phase polymorphism: two highly ordered tilted phases CrG* and SmI*, as well as the ferroelectric smectic C (SmC*) and chiral nematic (N*) phase. In this series, the seldom observed transition between the chiral phases SmI*–SmC* is seen. All the compounds possess stable enantiotropic SmC* and N* phases. The existence of weak intermolecular hydrogen-bonding in (S)-MHOBSn was confirmed by FTIR spectroscopy. 相似文献
10.
Enantiomeric amide derivatives of (S)- and (R)-1-phenyl-2-aminopropane (dextro- and levoamphetamine, respectively) were resolved by high performance liquid chromatography on commercially available ionically and covalently bonded chiral stationary phases ((R)-N-(3,5-dinitrobenzoyl)phenylglycine). Ten enantiomeric amide pairs were synthesized and chromatographed on the columns by using a mobile phase of hexane-isopropanol (97 : 3), a flow rate of 2 ml/min, and a column temperature of 20°C. The (R)-isomer of all 10 amides eluted first on the covalent column as did the (R)-isomer of nine derivatives on the ionic column. however, the 3,5-dinitrobenzoyl amide of (S)- amphetamine eluted before the (R)-isomer on the ionic column. This reversal in enantiomeric elution order reveals the complexity of the interactions occurring on these columns and emphasizes the hazards of relying on observed elution order as an a priori indication of absolute configuration. 相似文献
11.
A new mixed crosslinking agent composed of dicumyl peroxide and tetra(methylvinyl)cyclotetrasiloxane was used to prepare fused silica capillary columns with in situ crosslinked stationary phases including PEG-20M, SE-54, and OV-1. These columns proved to have good thermostability and inertness. As examples of potential applications a mixture of isomers of nitrotoluene and dinitrotoluene, and pyrolyzates of polystyrene were separated by using these columns. 相似文献
12.
Han X Wang C He L Beesley TE Armstrong DW 《Analytical and bioanalytical chemistry》2007,387(8):2681-2697
A new synthetic polymeric chiral stationary phase for liquid chromatography was prepared via free-radical-initiated polymerization
of trans-9,10-dihydro-9,10-ethanoanthracene-(11S,12S)-11,12-dicarboxylic acid bis-4-vinylphenylamide. The new polymeric chiral stationary phase (CSP) showed enantioselectivity
for many chiral compounds in multiple mobile phases. High stability and sample capacities were observed on this polymeric
chiral stationary phase. Mobile phase components and additives affected chiral separation greatly. This new synthetic chiral
stationary phase is complementary to two other related commercially available CSPs: the P-CAP and P-CAP-DP columns. Interactions
between the chiral stationary phase and analytes that lead to retention and chiral recognition include hydrogen bonding, dipolar,
and π–π interactions. Repulsive (steric) interactions also contribute to chiral recognition.
Figure LC chromatograms showing the analytical (blue) and preparative (red) separations of N-(3,5-dinitrobenzoylleucine) enantiomers on a new synthetic polymeric chiral stationary phase 相似文献
13.
T. Benincori R. Cirilli R. Ferretti F. La Torre O. Piccolo L. Zanitti 《Chromatographia》2002,55(1-2):25-31
Summary Resolution of the enantiomers of new racemic diphosphines, which are very useful ligands for stereoselective catalysts, and
of the corresponding phosphine oxides has been investigated by high-performance liquid chromatography (HPLC) on four different
chiral stationary phases (CSP)—Chiralpak AD, Whelk-01, and Supelcosil naphthylurea and phenylurea columns. The mobile phases
were optimized to achieve separation of the enantiomers. α andR
S values ranged from 1.05 to 5.17 and from 0.37 to 6.57, respectively, for the Chiralpak AD and (R,R)-Whelk-01 columns. For the Supelcosil LC-(R)-phenylurea and Supelcosil LC-(S)-naphthylurea columns α values ranged from 1.05 to 1.62 andR
S from 0.35 to 3.61. 相似文献
14.
S. Boneva 《Chromatographia》1987,23(1):50-52
Summary Gas chromatographic retention indices for 16 C6 alkanols measured on capillary columns coated with OV-101 methylsilicone and Carbowax 20M propylethyleneglycol liquid phases at 80° and 90°C were determined. The respective standard deviation values were 0.5 and 0.8 i.u. The correlation between the retention indices measured on non-polar and polar stationary phases and the boiling points of the alkanols was studied. 相似文献
15.
Crosslinking experiments for the chiral stationary phase OV-225-L-Val-t-butylamide within both fused silica and glass capillary columns have been carried out. Amino acid enantiomers were separated on crosslinked columns by both GC and SFC methods. In SFC, the a values of amino acid enantiomers are independent of the density of the mobile phase, and they are hig her than those obtained by GC for the tested enantiomers with the same column due to the lower column temperature used in SFC. 相似文献
16.
Ilyas S. Nizamov Georgiy G. Shumatbaev Ilnar D. Nizamov Yevgeniy N. Nikitin Timur G. Belov Marina P. Shulaeva 《Phosphorus, sulfur, and silicon and the related elements》2021,196(1):86-92
Abstract New chiral methylbenzylammonium salts of aryldithiophosphonic acids containing glucofuranose, allofuranose, and galactopyranose diacetonide substituents were obtained using (S)-(–)-α-methylbenzylamine, (R)-(+)-α-methylbenzylamine, and (R,S)-(±)-α-methylbenzylamine. Salts obtained possess antimicrobial activity. 相似文献
17.
(1R,2R,3R,4S,5R)-4-amino-5-methylcyclopentane-1,2,3-triol ( 1 ) was prepared stereoselectively from D -ribose (Scheme). Aminocyclopentanetriol 1 , which by its design may be considered an analog of the fucosyl cation, inhibits α-L -fucosidase selectively (Ki=28 μM ) over α- and β-glucosidase, α- and β-mannosidase, and α- and β-galactosidase (Table). 相似文献
18.
(R)- and (S)-α-ionone ((R)- and (S)- 1 , resp.) were prepared from (R)- and (S)-α-damascone ((R)- and (S)- 3 , resp.) without racemization in 48% yield employing a new enone transposition. The described transposition is complementary to existing methods whose application is often prohibited by the structural requirements of the substrate. The now easily accessible α-ionones of desired absolute configuration are useful as chiral building blocks for terpenoid synthesis. 相似文献
19.
Payagala T Wanigasekara E Armstrong DW 《Analytical and bioanalytical chemistry》2011,399(7):2445-2461
Three new polymeric chiral stationary phases were synthesized based on (1S,2S)-1,2-bis(2,4,6-trimethylphenyl)ethylenediamine, (1S,2S)-1,2-bis(2-chlorophenyl)ethylenediamine, and (1S,2S)-1,2-di-1-naphthylethylenediamine via a simple free-radical-initiated polymerization in solution. These monomers are structurally
related to (1S,2S)-1,2-diphenylethylenediamine which is the chiral monomer used for the commercial P-CAP-DP polymeric chiral stationary phase
(CSP). The performance of these three new chiral stationary phases were evaluated in normal phase high-performance liquid
chromatography (HPLC) and supercritical fluid chromatography and the results were compared with those of the P-CAP-DP column.
All three new phases showed enantioselectivity for a large number of racemates with a variety of functional groups, including
amines, amides, alcohols, amino acids, esters, imines, thiols, and sulfoxides. In normal phase, 68 compounds were separated
with 28 baseline separations (Rs ≥ 1.5) and in SFC, 65 compounds were separated with 24 baseline separations. In total 72
out of 100 racemates were separated by these CSPs with 37 baseline separations. Complimentary separation capabilities were
observed for many analytes. The new polymeric CSPs showed similar or better enantioselectivities compared with the commercial
column in both HPLC and SFC. However, faster separations were achieved on the new stationary phases. Also, it was shown that
these polymeric stationary phases have good sample loading capacities while maintaining enantioselectivity. 相似文献
20.
Both enantiomers of inherently chiral calixarene carboxylic acids with ABCD substitution patterns have been prepared by the benzoylation of 25-propoxy-27-(R)-N-(α-phenylethyl)amidomethyloxycalix[4]arene followed by resolution of the diastereomers formed, monobromination of them and removal of the benzoyl and α-phenylethylamide auxiliary groups. The absolute configuration of the calixarenes obtained has been established by X-ray analysis. Preliminary study of the chiral recognition properties of calixarene carboxylic acid was performed. 相似文献