Reversal of the Leloir pathway to promote galactose and tagatose synthesis from glucose
Source abstract
Abstract
D-Tagatose is a low-calorie rare sugar with health benefits as a low-glycemic sweetener. Current production methods are limited, often relying on galactose isomerization, and remain inefficient and costly. Here, we report a whole-cell process in Escherichia coli that converts glucose directly to tagatose by reversing the Leloir pathway. Central to this approach is a galactose-1-phosphate-specific phosphatase that drives equilibrium toward galactose. Computational analyses reveal hydrogen-bond networks that underlie stringent substrate selectivity. By co-expressing this phosphatase with an L-arabinose isomerase in a metabolically engineered strain, we demonstrate direct glucose-to-tagatose conversion. Cultures produced ∼10.5 g/L galactose from 30 g/L glucose (35% yield) and >1 g/L tagatose. While this is a proof-of-principle demonstration and further optimization is required to improve tagatose production, this strategy eliminates dependence on lactose-derived galactose and provides a framework for scalable, glucose-based biosynthesis of tagatose and other galactose-derived molecules, supporting sustainable rare-sugar production.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Diet, Metabolism, and Disease · Carbohydrate Chemistry and Synthesis · Cancer, Hypoxia, and Metabolism
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (79)
Show source-provided references
1. Current studies on biological tagatose production using l-arabinose isomerase: a review and future perspective10.1007/s00253-004-1665-8 ↗
2. Tagatose, the New GRAS Sweetener and Health Product10.1089/109662002753723197 ↗
3. Lactose-Derived Nondigestible Oligosaccharides and Other High Added-Value Products
4. Tagatose: properties, applications, and biotechnological processes10.1007/s00253-007-0981-1 ↗
5. Bioconversion of d-galactose into d-tagatose10.1016/0141-0229(93)90032-W ↗
6. Galactose to tagatose isomerization at moderate temperatures with high conversion and productivity10.1038/s41467-019-12497-8 ↗
7. Production of d-tagatose in packed bed reactor containing an immobilized l-arabinose isomerase on alginate support10.1016/j.bcab.2021.102227 ↗
8. Overcoming the thermodynamic equilibrium of an isomerization reaction through oxidoreductive reactions for biotransformation10.1038/s41467-019-09288-6 ↗
9. Efficient production of d-tagatose via DNA scaffold mediated oxidoreductases assembly in vivo from whey powder10.1016/j.foodres.2023.112637 ↗
10. High-yield production of pure tagatose from fructose by a three-step enzymatic cascade reaction10.1007/s10529-017-2340-3 ↗
11. Development of Tagaturonate 3-Epimerase into Tagatose 4-Epimerase with a Biocatalytic Route from Fructose to Tagatose10.1021/acscatal.0c02922 ↗
12. Polyols in confectionery: the route to sugar-free, reduced sugar and reduced calorie confectionery10.1079/BJN2000260 ↗
13. USDA Economic Research Service (2024). World, U.S., and Mexican Sugar and Corn Sweetener Prices. https://www.ers.usda.gov/data-products/sugar-and-sweeteners-yearbook-tables/.
14. USDA Economics Statistics and Market Information System (2024). Lactose Prices Graph. https://usda.library.cornell.edu/concern/publications/j9602j75h?locale=en.
15. Biosynthesis of a healthy natural sugar D-tagatose: advances and opportunities10.1080/07388551.2025.2489424 ↗
16. Structure-based prediction and identification of 4-epimerization activity of phosphate sugars in class II aldolases10.1038/s41598-017-02211-3 ↗
17. A critical comparison of cellular and cell-free bioproduction systems10.1016/j.copbio.2019.05.003 ↗
18. Structure and Function of Enzymes of the Leloir Pathway for Galactose Metabolism10.1074/jbc.R300025200 ↗
19. Control of the galactose-to-glucose consumption ratio in co-fermentation using engineered Escherichia coli strains10.1038/s41598-020-69143-3 ↗
20. Novel In Vitro Multienzyme Cascade for Efficient Synthesis of d-Tagatose from Sucrose10.3390/catal13121515 ↗
21. Novel Activity of UDP-Galactose-4-Epimerase for Free Monosaccharide and Activity Improvement by Active Site-Saturation Mutagenesis10.1007/s12010-010-9052-7 ↗
22. Discovery of a Kojibiose Phosphorylase in Escherichia coli K-1210.1021/acs.biochem.8b00392 ↗
23. Structural basis for broad substrate specificity of UDP-glucose 4-epimerase in the human milk oligosaccharide catabolic pathway of Bifidobacterium longum10.1038/s41598-019-47591-w ↗
24. Galactose to tagatose isomerization by the l-arabinose isomerase from Bacillus subtilis: A biorefinery approach for Gelidium sesquipedale valorisation10.1016/j.lwt.2021.112199 ↗
25. Characterization of l-Arabinose Isomerase from Klebsiella pneumoniae and Its Application in the Production of d-Tagatose from d-Galactose10.3390/app12094696 ↗
26. Standard Gibbs energy of metabolic reactions: II. Glucose-6-phosphatase reaction and ATP hydrolysis10.1016/j.bpc.2017.02.005 ↗
27. Production of d-tagatose at high temperatures using immobilized Escherichia coli cells expressing l-arabinose isomerase from Thermotoga neapolitana10.1007/s10529-006-9277-2 ↗
28. EQuilibrator 3.0: A database solution for thermodynamic constant estimation10.1093/nar/gkab1106 ↗
29. Brain inositol monophosphatase identified as a galactose 1-phosphatase10.1016/S0006-8993(97)01042-1 ↗
30. A highly specific L-galactose-1-phosphate phosphatase on the path to ascorbate biosynthesis10.1073/pnas.0407453101 ↗
31. Differential Selectivity of the Escherichia coli Cell Membrane Shifts the Equilibrium for the Enzyme-Catalyzed Isomerization of Galactose to Tagatose10.1128/AEM.02691-07 ↗
32. Characterization of an L-arabinose isomerase from Bacillus coagulans NL01 and its application for D-tagatose production10.1186/s12896-016-0286-5 ↗
33. Improving Product Yields on D-Glucose in Escherichia coli Via Knockout of pgi and zwf and Feeding of Supplemental Carbon Sources10.1002/bit.25470 ↗
34. Carbon catabolite repression relaxation in Escherichia coli: global and sugar-specific methods for glucose and secondary sugar co-utilization10.1016/j.coche.2020.05.005 ↗
35. l -arabinose isomerases: Characteristics, modification, and application10.1016/j.tifs.2018.05.016 ↗
36. Glucose Transport in Escherichia coli: From Basics to Transport Engineering10.3390/microorganisms11061588 ↗
37. Identification and Analysis of the Putative Pentose Sugar Efflux Transporters in Escherichia coli10.1371/journal.pone.0043700 ↗
38. Gene Dispensability in Escherichia coli Grown in Thirty Different Carbon Environments10.1128/mBio.02259-20 ↗
39. Repression of galP , the galactose transporter in Escherichia coli , requires the specific regulator of N -acetylglucosamine metabolism10.1111/j.1365-2958.2008.06515.x ↗
40. Accurate structure prediction of biomolecular interactions with AlphaFold 310.1038/s41586-024-07487-w ↗
41. Structural Studies of Metal Binding by Inositol Monophosphatase: Evidence for Two-Metal Ion Catalysis10.1021/bi00198a012 ↗
42. ONIOM (DFT:MM) Study of the Catalytic Mechanism of myo -Inositol Monophosphatase: Essential Role of Water in Enzyme Catalysis in the Two-Metal Mechanism10.1021/jp312483n ↗
43. Structure and mechanism of inositol monophosphatase10.1016/0014-5793(95)00063-F ↗
44. Mobile loop mutations in an archaeal inositol monophosphatase: Modulating three-metal ion assisted catalysis and lithium inhibition10.1002/pro.315 ↗
45. Insights into the Role of Magnesium Triad in myo -Inositol Monophosphatase: Metal Mechanism, Substrate Binding, and Lithium Therapy10.1021/ci300172r ↗
46. Whole-cell biosynthesis of d-tagatose from maltodextrin by engineered Escherichia coli with multi-enzyme co-expression system10.1016/j.enzmictec.2021.109747 ↗
47. Activating the D-Tagatose Production Capacity of Escherichia coli with Structural Insights into C4 Epimerase Specificity10.1021/acs.jafc.4c12842 ↗
48. Efficient production of D-tagatose through cell membrane permeabilization modification and multi-enzymes compartmentalization10.1016/j.ijbiomac.2025.147878 ↗
49. Deciphering the structural basis of the broad substrate specificity of myo-inositol monophosphatase (IMP) from Cicer arietinum10.1016/j.ijbiomac.2019.11.098 ↗
50. Multibody cofactor and substrate molecular recognition in the myo-inositol monophosphatase enzyme10.1038/srep30275 ↗
51. Engineering Escherichia coli for D-allulose biosynthesis from glycerol10.1016/j.jbiotec.2024.08.012 ↗
52. MAFFT Multiple Sequence Alignment Software Version 7: Improvements in Performance and Usability10.1093/molbev/mst010 ↗
53. FastTree 2 – Approximately Maximum-Likelihood Trees for Large Alignments10.1371/journal.pone.0009490 ↗
54. One-step inactivation of chromosomal genes in Escherichia coli K-12 using PCR products10.1073/pnas.120163297 ↗
55. Positive and negative selection using the tetA-sacB cassette: recombineering and P1 transduction in Escherichia coli10.1093/nar/gkt1075 ↗
56. The structure assessment web server: for proteins, complexes and more10.1093/nar/gkae270 ↗
57. AutoDock4 and AutoDockTools4: Automated docking with selective receptor flexibility10.1002/jcc.21256 ↗
58. UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations10.1021/ja00051a040 ↗
59. Avogadro: an advanced semantic chemical editor, visualization, and analysis platform10.1186/1758-2946-4-17 ↗
60. UCSF ChimeraX: Structure visualization for researchers, educators, and developers10.1002/pro.3943 ↗
61. UCSF ChimeraX: Tools for structure building and analysis10.1002/pro.4792 ↗
62. UCSF ChimeraX: Meeting modern challenges in visualization and analysis10.1002/pro.3235 ↗
63. Improved side-chain torsion potentials for the Amber ff99SB protein force field10.1002/prot.22711 ↗
64. GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers10.1016/j.softx.2015.06.001 ↗
65. Comparison of simple potential functions for simulating liquid water10.1063/1.445869 ↗
66. Particle mesh Ewald: An N ⋅log( N ) method for Ewald sums in large systems10.1063/1.464397 ↗
67. LINCS: A linear constraint solver for molecular simulations10.1002/(SICI)1096-987X(199709)18:12<1463::AID-JCC4>3.0.CO;2-H ↗
68. Recent developments in the general atomic and molecular electronic structure system10.1063/5.0005188 ↗
69. ACPYPE - AnteChamber PYthon Parser interfacE10.1186/1756-0500-5-367 ↗
70. AmberTools10.1021/acs.jcim.3c01153 ↗
71. VMD: Visual molecular dynamics10.1016/0263-7855(96)00018-5 ↗
72. Escaping free-energy minima10.1073/pnas.202427399 ↗
73. PLUMED: A portable plugin for free-energy calculations with molecular dynamics10.1016/j.cpc.2009.05.011 ↗
74. QwikMD 2.0: bridging the gap between sequence, structure, and protein function10.1016/j.bpj.2021.11.2041 ↗
75. CHARMM36 all-atom additive protein force field: Validation based on comparison to NMR data10.1002/jcc.23354 ↗
76. CHARMM general force field: A force field for drug-like molecules compatible with the CHARMM all-atom additive biological force fields10.1002/jcc.21367 ↗
77. Structure and Dynamics of the TIP3P, SPC, and SPC/E Water Models at 298 K10.1021/jp003020w ↗
78. Stewart, J.J. Stewart Computational Chemistry - MOPAC (2007) Home Page http://openmopac.net/
79. Scalable molecular dynamics on CPU and GPU architectures with NAMD10.1063/5.0014475 ↗