Research Milestones

1977: Early description of the use of glycolytic enzymes in the synthesis of stable isotopically labeled carbohydrates

• H. A. Nunez, T. E. Walker, R. Fuentes, J. O'Connor, A. Serianni and R. Barker, Carbon-13 As a Tool For the Study of Carbohydrate Structures, Conformations and Interactions, J. Supramol. Structure 6, 1977, 535.

1979: Description of the cyanohydrin reduction method for ¹³C-labeling of aldohexoses, aldopentoses, aldotetroses, glyceraldehyde and glycolaldehyde

• A. S. Serianni, H. A. Nunez and R. Barker, Carbon-13 Enriched Carbohydrates: Preparation of Aldononitriles and Their Reduction with a Palladium Catalyst, Carbohydr. Res. 72, 1979, 71.
• A. S. Serianni, E. L. Clark and R. Barker, Carbon-13 Enriched Carbohydrates: Preparation of Erythrose, Threose, Glyceraldehyde and Glycolaldehyde with [¹³C]-Enrichment in Various Carbon Atoms, Carbohydr. Res. 72, 1979, 79.

1980: Modification of the cyanohydrin reduction method to prepare ²H-labeled aldoses

A. S. Serianni and R. Barker, Isotopically-Enriched Carbohydrates: The Preparation of [²H]-Enriched Aldoses by Catalytic Hydrogenolysis of Cyanohydrins with ²H₂, Can. J. Chem. 57, 1979, 3160.

1980: Description of the integrated use of trans-O-glycoside ³J_COCH and ³J_COCC in oligosaccharide conformational analysis

• M. L. Hayes, A. S. Serianni and R. Barker, Methyl Lactoside: 600 MHz ¹H and 75 MHz ¹³C NMR Studies of ²H and ¹³C-Enriched Compounds, Carbohydr. Res. 100, 1982, 87.

1982: Description of NMR saturation-transfer to measure unidirectional rate constants of anomerization of aldofuranoses; structure/reactivity relationships in furanose anomerization

• A. S. Serianni, J. Pierce, S. Huang and R. Barker, Anomerization of Furanose Sugars: Kinetics of Ring-Opening Reactions by ¹H and ¹³C Saturation-Transfer NMR Spectroscopy, J. Am. Chem. Soc. 104, 1982, 4037.

1982: Elucidation of unique molybdate-catalyzed rearrangement mechanism of aldose C2-epimerization

• M. L. Hayes, N. J. Pennings, A. S. Serianni, and R. Barker, Epimerization of Aldoses by Molybdate Involving a Novel Rearrangement of the Carbon Skeleton, J. Am. Chem. Soc. 104, 1982, 6764.

1982: Description of the use of enzymes in the synthesis of various isotopically labeled saccharides

• A. S. Serianni, E. Cadman, J. Pierce, M. L. Hayes and R. Barker, Enzymatic Synthesis of Isotopically-Enriched Aldoses, Ketoses and their Phosphate Esters, Methods in Enzymology 89, Part D, W. Wood, Ed., 1982, 83.

1982: Commercialization of the cyanohydrin reduction technology; founding of Omicron Biochemicals, Inc.

1983: Synthesis of saccharides containing chiral (deuterated) hydroxymethyl groups

• G. Wu, A. S. Serianni and R. Barker, Stereospecific Exchange of Methylene Protons in Tetrofuranosides: Hydroxymethyl Group Conformations in Pentofuranosides, J. Org. Chem. 48, 1983, 1750.

1984: Description of the integrated use of J_HH, J_CH and J_CC in the conformational analysis of furanosyl rings

• A. S. Serianni and R. Barker, [¹³C]-Enriched Tetroses and Tetrofuranosides: An Evaluation of the Relationship Between NMR Parameters and Furanosyl Ring Conformation, J. Org. Chem. 49, l984, 3292.

1986: Experimental measurements of unidirectional rates of anomerization in aldopyranoses

• J. R. Snyder and A. S. Serianni, D-Idose: A One- and Two-Dimensional NMR Investigation of Solution Composition and Conformation, J. Org. Chem. 51, 1986, 2694.

1987-1992: Systematic investigations of J_CC in aldoses

• M. J. King-Morris and A. S. Serianni, ¹³C NMR Studies of [1-¹³C]Aldoses: Empirical Rules Correlating Pyranose Ring Configuration and Conformation With ¹³C Chemical Shifts and ¹³C-¹³C Spin Couplings, J. Am. Chem. Soc. 109, 1987, 3501.
• J. Wu, P. B. Bondo, T. Vuorinen and A. S. Serianni, ¹³C-¹³C Spin Coupling Constants in Aldoses Enriched with ¹³C at the Terminal Hydroxymethyl Carbon: Effect of Coupling Pathway Structure on J_CC in Carbohydrates, J. Am. Chem. Soc., 114, 1992, 3499.

1987: First molecular orbital calculations on intact aldofuranose rings

• A. S. Serianni and D. M. Chipman, Furanose Ring Conformation: Application of Ab Initio Molecular Orbital Calculations To the Structure and Dynamics of the Erythrofuranose and Threofuranose Rings, J. Am. Chem. Soc. 109, 1987, 5297.

1988-1990: Synthesis and NMR investigations of nucleosides containing chiral hydroxymethyl groups

• P. C. Kline and A. S. Serianni, Chiral Hydroxymethyl Groups: ¹H NMR Assignments of the Prochiral C5' Protons of Ribonucleosides, Mag. Reson. Chem. 26, 1988, 120.
• P. C. Kline and A. S. Serianni, Chiral Hydroxymethyl Groups: ¹H NMR Assignments of the Prochiral C5' Protons of 2'-Deoxyribonucleosides, Mag. Reson. Chem., 28, 1990, 324.

1988-1994: In vivo NMR studies of freeze tolerance in lepidoptera

• O. Kukal, A. S. Serianni and J. Duman, Glycerol Metabolism in a Freeze-tolerant Arctic Insect: an in vivo ¹³C NMR Study, J. Comp. Physiol. B 158, 1988, 175.
• O. Kukal, J. G. Duman and A. S. Serianni, Cold-Induced Mitochondrial Degradation and Cryoprotectant Synthesis in Freeze-Tolerant Arctic Caterpillars, J. Comp. Physiol. B 158, 1989, 661.
• C. Podlasek and A. S. Serianni, ¹⁹F and ¹³C NMR Studies of Polyol Metabolism in Freeze-Tolerant Pupae of Hyalophora cecropia, J. Biol. Chem., 269, 1994, 2521.

1990-1997: NMR studies of J_CH and J_CC in nucleosides

• P. C. Kline and A. S. Serianni, [¹³C]-Enriched Ribonucleosides: Synthesis and Application of ¹³C-¹H and ¹³C-¹³C Spin-Coupling Constants to Assess Furanose and N-Glycoside Bond Conformations, J. Am. Chem. Soc., 112, 1990, 7373.
• P. C. Kline and A. S. Serianni, [¹³C]-Substituted Erythronucleosides: Synthesis and Conformational Analysis by ¹H and ¹³C NMR Spectroscopy, J. Org. Chem., 57, 1992, 1772.
• T. Bandyopadhyay, J. Wu and A. S. Serianni, [1'-¹³C]2'-Deoxyribonucleosides: Structural and Conformational Insights Derived from ¹³C-¹H Spin Coupling Constants Involving C1', J. Org. Chem., 58, 1993, 5513.
• T. Bandyopadhyay, J. Wu, W.A. Stripe, I. Carmichael and A.S. Serianni, ¹³C-¹H and ¹³C-¹³C Spin Couplings in [2'-¹³C]2'-Deoxyribonucleosides: Correlations with Molecular Structure, J. Am. Chem. Soc., 119, 1997, 1737-1744.

1990: Development of an automated synthesizer of labeled saccharides

• U. L. Stafford, A. S. Serianni and A. Varma, Microcomputer Automated Synthesis of Stable Isotopically Labeled Monosaccharides, American Institute of Chemical Engineering Journal, 36, 1990, 1822.

1988-1991: Studies of Thorpe-Ingold effects in aldoses; refined structure/reactivity relationships in furanose and pyranose anomerization; synthesis of labeled ketoses; ketose anomerization

• J. Wu, T. Vuorinen and A. S. Serianni, Furanose Ring Anomerization: Kinetic and Thermodynamic Studies of the D-2-Pentuloses by ¹³C NMR Spectroscopy, Carbohydr. Res., 206, 1990, 1.
• T. Vuorinen and A. S. Serianni, Synthesis of D-erythro-2-Pentulose and D-threo-2-Pentulose: Analysis of ¹³C and ¹H NMR Spectra of [1-¹³C]- and [2-¹³C]-Substituted Compounds, Carbohydr. Res., 209, 1990, 13.

1990-1992: Description of cross-peak displacement method for measuring J-couplings in saccharides; use of homonuclear 2D J-spectroscopy to measure J_CH in labeled saccharides; use of 2D ¹³C exchange spectroscopy to measure overall rates of amomerization; application of DESERT method in oligosaccharide conformational analysis.

• P. C. Kline, S.-G. Huang, M. L. Hayes, R. Barker and A. S. Serianni, Internuclear ¹H-¹H Distance Measurements in Carbohydrates: Proton Transient Nuclear Overhauser Enhancement and Spin-Lattice Relaxation in [¹³C]- and [²H]-Substituted Compounds, Can. J. Chem., 68, 1990, 2171.
• T. Vuorinen and A. S. Serianni, [¹³C]-Substituted Pentos-2-uloses: Synthesis and Analysis by ¹H and ¹³C NMR Spectroscopy, Carbohydr. Res., 207, 1990, 185.
• J. Wu and A. S. Serianni, Isotope-Edited 1D and 2D NMR Spectroscopy of [¹³C]-Substituted Carbohydrates, Carbohydr. Res., 226, 1992, 209.

1993: First investigation of ¹J_CC in saccharides; correlations with molecular torsion angles

• I. Carmichael, D. M. Chipman, C. A. Podlasek and A. S. Serianni, Torsional Effects on the One-Bond ¹³C-¹³C Spin Coupling Constant in Ethylene Glycol: Insights into the Behavior of ¹J_CC in Carbohydrates, J. Am. Chem. Soc., 115, 1993, 10863.

1994: First NMR study of site-specifically labeled oligodeoxyribonucleotides (CCAAT sequences)

• J. Wu and A. S. Serianni, [¹³C]-Labeled Oligodeoxyribonucleotides: A Solution Study of a CCAAT-Containing Sequence at the NF-I Recognition Site of Human Adenovirus, Biopolymers, 34, 1994, 1175.

1995: Systematic study of J_CH in methyl aldopyranosides

• C. A. Podlasek, J. Wu, W. A. Stripe, P. B. Bondo and A. S. Serianni, [¹³C]-Enriched Methyl Aldopyranosides: Structural Interpretation of ¹³C-¹H Spin-Coupling Constants and ¹H Chemical Shifts, J. Am. Chem. Soc., 117, 1995, 8635.

1995: Description of ¹J_CH as a conformational probe in aldofuranosyl rings

• A. S. Serianni and I. Carmichael, One-Bond ¹³C-¹H Spin-Coupling Constants in Aldofuranosyl Rings: Effects of Conformation on Coupling Magnitude, J. Am. Chem. Soc., 117, 1995, 8645.

1996-2000: Introduction of the projection resultant rule to interpret ²J_COC in saccharides; measurement of ²J_CCC and ²J_COC coupling signs by ¹³C-¹³C COSY-45 in triply-labeled saccharides; elucidation of the effect of COC bond-angle on ²J_COC magnitude

• T. Church and A. S. Serianni, Two-bond ¹³C-¹³C Spin-Coupling Constants in Carbohydrates: Effect of Structure on Coupling Magnitude and Sign, Carbohydr. Res., 280, 1996, 177.
• A.S. Serianni, P.B. Bondo and J. Zajicek, Two-Bond ¹³C-¹³C Coupling Sign Determinations in Carbohydrates: Verification of the Projection Resultant Method, J. Magn. Reson. Series B, 112, 1996, 69.
• S. Zhao, G. Bondo, J. Zajicek and A.S. Serianni, Two-Bond ¹³C-¹³C Spin-Coupling Constants in Carbohydrates: New Measurements of Coupling Signs, Carbohydr. Res., 309, 1998, 145-152.
• F. Cloran, I. Carmichael and A.S. Serianni, ²J_COC Spin-Coupling Constants Across Glycosidic Linkages Exhibit a Valence Bond-Angle Dependence, J. Am. Chem. Soc. 2000, 122, 396-397.

1996-1997: First systematic experimental and theoretical analyses of J_CH and J_CC in the beta-D-ribofuranosyl and 2-deoxy-beta-D-ribofuranosyl rings

• C. A. Podlasek, W. A. Stripe, I. Carmichael, M. Shang, B. Basu and A.S. Serianni, ¹³C-¹H Spin-Coupling Constants in the beta-D-Ribofuranosyl Ring: Effect of Ring Conformation on Coupling Magnitudes, J. Am. Chem. Soc., 118, 1996, 1413.
• T.J. Church, I. Carmichael, and A.S. Serianni, ¹³C-¹H and ¹³C-¹³C Spin-Coupling Constants in Methyl beta-D-Ribofuranoside and Methyl 2-Deoxy-beta-D-erythro-pentofuranoside: Correlation with Molecular Structure and Conformation, J. Am. Chem. Soc., 119, 1997, 8946-8964.

1997-2000: Quantum mechanical studies of the effect of ring-oxygen and N1 protonation on the molecular structures of aldofuranoses and aldofuranosylamines

• J. Kennedy, J. Wu, K. Drew, I. Carmichael and A.S. Serianni, Carbohydrate Reaction Intermediates: Effect of Ring Oxygen Protonation on the Structure and Conformation of Aldofuranosyl Rings, J. Am. Chem. Soc., 119, 1997, 8933-8945.
• F. Cloran, I. Carmichael and A.S. Serianni, 2-Deoxy-beta-D-erythro-pentofuranosylamine: Quantum Mechanical Calculations of Molecular Structure and NMR Spin-Spin Coupling Constants in Nitrogen-Containing Saccharides, J. Am. Chem. Soc. 2000, 122, 6435-6448.

1998: Quantification of cyclic and acyclic forms of aldopentoses in solution; description of isotope-edited HMQC-TOCSY applications in saccharides

• K.N. Drew, J. Zajicek, G. Bondo, B. Bose and A.S. Serianni, ¹³C-Labeled Aldopentoses: Detection and Quantitation of Cyclic and Acyclic Forms by 1D and 2D Heteronuclear NMR Spectroscopy, Carbohydr. Res., 307, 1998, 199-209.

1998: Development of a new Karplus relationship for ³J_COCC in saccharides; applications in oligosaccharides

• B. Basu, S. Zhao, P. Bondo, G. Bondo, F. Cloran, I. Carmichael, R. Stenutz, B. Hertz and A.S. Serianni, Three-Bond C-O-C-C Spin-Coupling Constants in Carbohydrates: Development of a Karplus Relationship, J. Am. Chem. Soc., 120, 1998, 11158-11173.

1999: First theoretical (DFT) treatment of ³J_COCC across O-glycosidic linkages

• F. Cloran, I. Carmichael and A.S. Serianni, DFT Calculations on Disaccharide Models: Studies of Molecular Geometries and Trans-O-Glycoside ³J_COCH and ³J_COCH Spin-Couplings, J. Am. Chem Soc. 1999, 121, 9843-9851.

2000: Studies of J_HH, J_CH and J_CC in conformationally-constrained Pt-saccharide complexes

• H. Junicke, A.S. Serianni and D. Steinborn, Platinum(IV)-Carbohydrate Complexes: Structure Determination Based on ¹H-¹H, ¹³C-¹H and ¹³C-¹³C Spin-Spin Coupling Constants, J. Org. Chem. 2000, 65, 4153-4161.

2000: First systematic investigation of ²H quadrupolar coupling constants in saccharides

• B. Bose-Basu, J. Zajicek, G. Bondo, S. Zhao, M. Kubsch, I. Carmichael, and A.S. Serianni, Deuterium Spin-Lattice Relaxation Times and Quadrupolar Coupling Constants in Isotopically-Labeled Saccharides, J. Magn. Reson. 2000, 144, 207-216.

2000: Theoretical study of N-substitution effects on structure, conformation and J-couplings in aldofuranoses

• F. Cloran, I. Carmichael and A.S. Serianni, 2-Deoxy-beta-D-erythro-pentofuranosylamine: Quantum Mechanical Calculations of Molecular Structure and NMR Spin-Spin Coupling Constants in Nitrogen-Containing Saccharides, J. Am. Chem. Soc. 2000, 122, 6435-6448.