The most recent version of the kinetic method, i.e. fixed ligand method, is applied towards chiral discrimination of three pairs of enantiomeric hexose monosaccharides under mass spectral conditions. Naturally occurring mononucleotides are used as fixed ligands (FL) and the amino acids are selected as the chiral references (ref) to discriminate the analyte (A), the enantiomers of glucose, mannose and galactose. Chiral discrimination is achieved by investigating the collision-induced dissociation spectra of trimeric complex ion, [NiII(FL)(ref)(A)–H]+ generated by electrospraying the solution mixture of d- or l-analyte (A), FL, amino acid (ref) and NiCl2. The relative abundance of product ions resulting from the competitive loss of reference amino acid and analyte are considered for measuring the degree of chiral discrimination by applying the kinetic method. l-Asp, l-Thr, l-Glu, l-Trp and l-Ser are found as suitable reference compounds. Among the tested mononucleotides (5′AMP, 5′GMP, 5′CMP, 5′UMP and 5′TMP), 5′GMP is found to be the best for the studied analytes. Chiral discrimination is found to depend on the nature of the monosaccharide, the functional groups present in the side chain of reference amino acids and the configuration of reference amino acids.
GrigoreanG.LebrillaC.B., “Enantiomeric analysis of pharmaceutical compounds by ion/molecule reactions”, Anal. Chem.73, 1684 (2001) doi: 10.1021/ac001135q
2.
CongX.CzerwieniecG.McJimpseyE.AhnS.TroyF.A.LebrillaC.B., “Structural relationships in small molecule interactions governing gas-phase enantioselectivity and zwitterionic formation”, J. Am. Soc. Mass Spectrom.17, 442 (2006). doi: 10.1016/j.jasms.2005.11.015
3.
AhnS.RamirezJ.GrigoreanG.LebrillaC.B., “Chiral recognition in gas-phase cyclodextrin: Amino acid complexes—is the three point interaction still valid in the gas phase?”, J. Am. Soc. Mass Spectrom.12, 278 (2001) doi: 10.1016/S1044-0305(00)00220-8
4.
RamirezJ.AhnS.GrigoreanG.LebrillaC.B., “Evidence for the formation of gas-phase inclusion complexes with cyclodextrins and amino acids”, J. Am. Chem. Soc.122, 6884 (2000). doi: 10.1021/ja000717m
5.
GrigoreanG.RamirezJ.AhnS.LebrillaC.B., “A mass spectrometry method for the determination of enantiomeric excess in mixtures of D,L-amino acids”, Anal. Chem.72, 4275 (2000). doi: 10.1021/ac000061f
6.
GalJ.F.StoneM.LebrillaC.B., “Chiral recognition of non-natural α-amino acids”, Int. J. Mass Spectrom.222, 259 (2003). doi: 10.1016/S1387-3806(02)00992-2
7.
BagheriH.ChenH.CooksR.G., “Chiral recognition by proton transfer reactions with optically active amines and alcohols”, Chem. Commun. 2740 (2004). doi: 10.1039/b410882e
8.
DeardenD.V.DejsupaC.LiangY.J.BradshawJ.S.IzattR.M., “Intrinsic contributions to chiral recognition: Discrimination between enantiomeric amines by dimethyldiketopyridino-18-crown-6 in the gas phase”, J. Am. Chem. Soc.119, 353 (1997). doi: 10.1021/ja962400i
9.
BottaB.BottaM.FilippiA.TafiA.MonacheG.D.SperanzaM., “Enantioselective guest exchange in a chiral resorcin[4]arene cavity”, J. Am. Chem. Soc.124, 7658 (2002). doi: 10.1021/ja020232t
10.
RamirezR.HeF.LebrillaC.B., “Gas-phase chiral differentiation of amino acid guests in cyclodextrin hosts”, J. Am. Chem. Soc.120, 7387 (1998). doi: 10.1021/ja9812251
11.
FilippiA.GasparriniF.PieriniM.SperanzaM.VillaniC., “Exceptional gas-phase enantioselectivity of chiral tetramide macrocycles”, J. Am. Chem. Soc.127, 11912 (2005). doi: 10.1021/ja0533038
12.
SawadaM., “Chiral recognition detected by fast atom bombardment mass spectrometry”, Mass Spectrom. Rev.16, 73 (1997). doi: 10.1002/(SICI)1098-2787(1997)16:2<73::AID-MAS2>3.0.CO;2-6
13.
KrishnaP.PrabhakarS.ManoharanM.JemmisE.D.VairamaniM., “Chiral recognition and the determination of optical purity of some amino acids ester salts using monosaccharides as chiral selectors under liquid secondary ion mass spectral conditions”, Chem. Commun. 1215 (1999). doi: 10.1039/a902366f
14.
KrishnaP.PrabhakarS.VairamaniM., “Chiral recognition and determination of optical purity of α-phenylethylamine using monosaccharide as a chiral selector under liquid secondary ion mass spectral conditions”Eur. J. Mass.Spectrom.5, 485 (1999). doi: 10.1255/ejms.312
15.
WuL.MeurerE.C.CooksR.G., “Chiral morphing and enantiomeric quantification in mixtures by mass spectrometry”, Anal. Chem.76, 663 (2004). doi: 10.1021/ac0349072
16.
AugustiD.V.CarazzaF.AugustiR.TaoW.A.CooksR.G., “Quantitative chiral analysis of sugars by electrospray ionization tandem mass spectrometry using modified amino acids as chiral reference compounds”, Anal. Chem.74, 3458 (2002). doi: 10.1021/ac020135i
17.
WuL.TaoW.A.CooksR.G., “Ligand and metal ion effects in metal ion clusters used for chiral analysis of α-hydroxy acids by the kinetic method”, Anal. Bioanal. Chem.373, 618 (2002). doi: 10.1007/s00216-002-1356-1
18.
NagaveniV.PrabhakarS.VairamaniM., “Differentiation of underivatized diastereomeric hexosamine monosaccharides and their quantification in a mixture using the kinetic method under electrospray ionization conditions”, Anal. Chem.76, 3505 (2004). doi: 10.1021/ac049829c
19.
KumarM. RaviPrabhakarS.VairamaniM., “Chiral discrimination of a-amino acids by the DNA triplet GCA”, Chem. Commun. 392 (2007). doi: 10.1039/b613232d
20.
KumariS.PrabhakarS.VairamaniM.DeviC.L.ChaitanyaG.K.BhanuprakashK., “Chiral discrimination of D- and L-amino acids using iodinated tyrosines as chiral references: Effect of iodine substituent”, J. Am. Soc. Mass Spectrom.18, 1516 (2007) doi: 10.1016/j.jasms.2007.05.006
21.
TaoW.A.CooksR.G., “Parallel reactions for enantiomeric quantification of peptides by mass spectrometry”, Angew. Chem. Int. Ed.40, 757 (2001). doi: 10.1002/1521-3773(20010216)40:4<757::AID-ANIE7570>3.0.CO;2-H
22.
KumariS.PrabhakarS.VairamaniM., “Halogen-substituted phenylalanines as enantioselective selectors for enantioselective discrimination of amino acids: Effect of halogen”, Rapid Commun. Mass Spectrom.22, 1393(2008). doi: 10.1002/rcm.3449
23.
SivaleelaT.KumarM. RaviPrabhakarS.BhaskarG.VairamaniM., “Chiral discrimination of a-amino acids by DNA tetranucleotides under electrospray ionzation conditions”, Rapid Commun. Mass Spectrom.22, 204 (2008). doi: 10.1002/rcm.3344
24.
TaoW.A.ZhangD.NikolaevE.N.CooksR.G., “Copper(II)-assisted enantiomeric analysis of D,L-amino acids using the kinetic method: Chiral recognition and quantification in the gas phase”, J. Am. Chem. Soc.122, 10598 (2000). doi: 10.1021/ja000127o
25.
WuL.CooksR.G., “Chiral analysis using the kinetic method with optimized fixed ligands: Applications to some antibiotics”, Anal. Chem.75, 678 (2003). doi: 10.1021/ac0260948
26.
LeeM.K.KumarA.P.JinD.LeeY.I., “Determination of enantiomeric compositions of DOPA by tandem mass spectrometry using the kinetic method with fixed ligands”, Rapid Commun. Mass Spectrom.22, 909 (2008). doi: 10.1002/rcm.3437
27.
GinsburgV., in Biological Mass Spectrometry, Ed by BurlingameA.L.McCloskeyJ.A., Elsevier, New York, USA (1990).
28.
ChipukJ.E.BrodbeltJ.S., “Gas-phase hydrogen/deuterium exchange of 5″- and 3″-mononucleotides in a quadrupole ion trap: Exploring the role of conformation and system energy”, J. Am. Soc. Mass Spectrom.18, 724 (2007). doi: 10.1016/j.jasms.2006.12.007
29.
WuL.CooksR.G., “Chiral and isomeric analysis by electrospray ionization and sonic spray ionization using the fixed-ligand kinetic method”, Eur. J Mass Spectrom.11, 231 (2005). doi: 10.1255/ejms.749
30.
GiddenJ.BowersM.T., “Gas-phase conformations of deprotonated and protonated mononucleotides determined by ion mobility and theoretical modeling”, J. Phys. Chem. B107, 12829 (2003). doi: 10.1021/jp035894z
31.
FletcherT.M.WalmsleyJ.A., “Stereospecific interactions of chiral cobalt(III)-amine complexes with guanosine 5″-monophosphate”, J. Inorg. Biochem.68, 239 (1997). doi: 10.1016/S0162-0134(97)00091-3
