Enantioseparation of dansyl amino acids by ultra-high pressure liquid chromatography using cationic β-cyclodextrins as chiral additives

This work reports the application of ultra-high pressure liquid chromatography (UHPLC) for reasonably fast enantiorecognition of some dansyl amino acids by employing three cationic β-cyclodextrins (β-CDs) as chiral additives. Good resolutions were obtained on an Agilent C18 column (2.1 mm i.d.; 1.8 μm; 50 mm length) with 1% (v/v) triethylammonium acetate buffered at pH 4.7 and acetonitrile as the mobile phase. Most of the analytes could be baseline resolved within 10 min. Increased cationic CD concentration or acetonitrile proportion in the mobile phase results in a decreased retention factor but accentuated selectivity. Furthermore, molecular mechanics calculation was performed and found to be consistent with the experimental results.     

Effect of metal ions on enantioseparation of five amino acids by ligand exchange capillary zone electrophoresisEI北大核心CSCD

Enantioseparation of five amino acids was conducted by chiral ligand exchange capillary zone electrophoresis (CLE-CZE). L-His and different metal ions in a certain proportion were used to form chiral recognition complexes. The enantiomers were exchanged with L-His ligands in the complex. Then, the separation of enantiomers was obtained according to the different ligand exchange ability. Effects of the valence and the electron layers of metal ions on the resolution were investigated systemically. Baseline separation of D, L-Phe, D, L-Tyr and D, L-Trp was obtained within 12 min when 4 mmol/L Co(Ⅱ) and 8 mmol/L L-His were added to the phosphate buffer solution (20 mmol/L, pH 8.0). The resolutions of D, L-Phe, D, L-Tyr and D, L-Trp were 1.53, 2.04, and 1.58, respectively. Partial chiral separation of D, L-Ser and D, L-Val was achieved under the same conditions. When Co(II) was used as the central ion, the resolution was better than that of Cu(II) and Zn(II), although they had the same number of electron layers and valence. The resolution of amino acids with Ag(I) as the central ion was not as good as that of divalent metal ions. Metal ions with three electron layers had better separation results than that with four electron layers. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

p-Nitrophenyl acetate hydrolysis promoted by Zn(II) and Co(II) complexes with the tripodal ligand of N,N′-bis(2-quinolinylmethyl)amantadine

To mimic the function of metallohydrolase, [M(bqad)Cl₂] (M = Zn(II) (1), Co(II) (2), where bqad = N,N′-bis(2-quinolinylmethyl)amantadine), have been synthesized and characterized by elemental analysis, electronic absorption, IR, and single crystal X-ray diffraction. The structural analysis indicated that metal ions in 1 and 2 were coordinated by three nitrogens from bqad and two chlorides, resulting in a distorted trigonal bipyramidal geometry. Kinetic experiments for hydrolytic cleavage of p-nitrophenyl acetate (pNA) catalyzed by 1 and 2 were performed at pH 7.50–10.00 and 298 K. The second-order rate constants (k_obs) increased exponentially with variation of pH values. The Co(II) complex exhibited potent catalytic activity.     

(l)- or (d)-Valine tert-butylamide grafted on permethylated β-cyclodextrin derivatives as new mixed binary chiral selectors: Versatile tools for capillary gas chromatographic enantioseparation

This work deals with the synthesis of two mixed binary chiral selectors prepared by grafting (l)- or (d)-valine tert-butylamide on permethylated cyclodextrin macrocycle. The enantioselective properties of the new chiral selectors diluted in OV11 polysiloxane (35% phenyl- and 65% methylsiloxane) were investigated by means of injections of 117 racemic mixtures. The mixed chiral selectors with (l)-valine and, to a lesser extent with (d)-valine, were found to have an improved enantioselectivity toward amino acid derivatives by comparison to permethylated cyclodextrin. The enantioseparation capability of these new chiral selectors has proven to be slightly less efficient than Chirasil-l-Val (Alltech) for amino acid derivatives, but it has been extended to include terpenes, lactones, esters, aliphatic compounds and aryl alcohols.     

Synthesis,crystal structure and magnetic properties of a new dinuclear copper(II) amino acid complex [Cu2(l-arg)2(μ-HPO4-O)(μ-HPO4-O,O′)(μ-OH)] · (H3O) · (H2O)6

A novel dinuclear copper(II) complex with the amino acid l-arginine (l-arg), with mono and bidentate HPO₄²⁻ oxoanions and an OH⁻ anion. [Cu₂(l-arg)₂(μ-HPO₄-O)(μ-HPO₄-O,O′)(μ-OH)]⁻ · (H₃O)⁺ · 6H₂O (1) was prepared and its structure was determined by X-ray diffraction methods. The two independent copper ions are in a distorted square pyramidal coordination, each bonded to one l-arginine molecule. These two Cu(l-arg) units are bridged by two monoatomic equatorial–apical oxygen ligands belonging to a monodentate hydrogenphosphate group, and to the hydroxyl group. The copper ions in the dinuclear unit at d = 3.1948(8) Å are also connected by two equatorial oxygen belonging to a bidentate hydrogenphosphate. This dinuclear character and bridging scheme, not common for metal–amino acid compounds, is a consequence of the properties of the phosphate anions. The magnetic susceptibility at temperatures between 2 and 300 K and the isothermal magnetization curves at T = 2.29(1) K with applied fields up to 9 T were measured. The magnetic data indicate an antiferromagnetic intradinuclear exchange coupling J/k_B = −3.7(1) K and using a molecular field approximation we estimated a weaker ferromagnetic interaction J′/k_B ∼ 0.3 K between neighbour dinuclear units.