Article
Chemistry, Multidisciplinary
Thomas Hansen, Tim P. Ofman, Joey G. C. Vlaming, Ivan A. Gagarinov, Jessey van Beek, Tessa A. Gote, Jacoba M. Tichem, Gijs Ruijgrok, Herman S. Overkleeft, Dmitri V. Filippov, Gijsbert A. van der Marel, Jeroen D. C. Codee
Summary: By systematically studying the reactivity-stereoselectivity relationships of caryophyllose donor and acceptor glycosides, using experimental and computational techniques, we were able to design carbohydrate building blocks with the necessary properties to assemble mycobacterial lipooligosaccharide fragments of M. marinum.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Weidong Shang, Dawen Niu
Summary: The study of carbohydrates has become important in various fields due to their pivotal roles in cellular processes. Chemical glycosylation reactions are highly needed to explore their biological functions. Recent advances in radical pathway glycosylation have shown great potential in developing novel methods for glycoside synthesis.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Organic
Kesatebrhan Haile Asressu, Chun-Wei Chang, Sarah Lam, Cheng-Chung Wang
Summary: Efforts to efficiently prepare sialosides have faced challenges in controlling the stereochemical outcome of sialylation reactions due to the unique chemical structure of sialic acid. A new strategy using Relative Reactivity Values (RRV) was developed to analyze six types of p-tolyl thiosialosides in sialylation reactions, revealing a correlation between alpha/beta stereoselectivity, yields, and intermediate changes with donor reactivity. These findings offer insights for tailoring suitable building blocks for stereo-controlled sialylation reactions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Sooyeon Moon, Sourav Chatterjee, Peter H. Seeberger, Kerry Gilmore
Summary: By quantifying the steric and electronic contributions of all chemical reagents and solvents through quantum mechanical calculations, a random forest algorithm was trained to accurately predict the stereoselective outcome of glycosylations. The model accurately predicts stereoselectivities for unseen nucleophiles, electrophiles, acid catalyst, and solvents across a wide temperature range, and was experimentally validated on a microreactor platform. This model helps identify novel ways to control glycosylation stereoselectivity and accurately predicts previously unknown means of stereocontrol.
Article
Chemistry, Multidisciplinary
Akira Yoshimura, Christopher D. Huss, Akio Saito, Tsugio Kitamura, Viktor V. Zhdankin
Summary: The presence of trifluoromethanesulfonic anhydride enhances the efficiency of 2-Iodosylbenzoic acid as an oxidant and electrophilic reagent for the preparation of alkenyl and aryliodonium salts, offering compatibility with acid-sensitive functional groups and mild reaction conditions resulting in higher yields.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Catherine Alex, Alexei V. Demchenko
Summary: This paper describes a new method for the direct, highly stereoselective synthesis of glycans containing beta-linked D-mannosaminuronic acid (ManNAcA) residues, including the capsular polysaccharide of Staphylococcus aureus type 8. The method achieves stereocontrol and introduces a way to achieve complete alpha-ManNAcA stereoselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Ananya Mukherji, Mahendra K. V. Rotta, Bikash K. Sarmah, Pavan K. Kancharla
Summary: This study investigates the influence of different silyl protecting groups (TBDMS, TIPS, and TBDPS) on 2-deoxyrhamnosylation. It is found that the TIPDS protecting group exhibits complete alpha-selectivity in C-glycosylation reactions. In contrast, the TBDPS protecting group shows superior protection for alpha-stereoselective O-glycosylation reactions with various acceptors.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Helle H. Trinderup, Sofie M. Andersen, Mads Heuckendorff, Henrik H. Jensen
Summary: The study showed that increasing the concentration and amount of triflic acid catalyst can enhance beta-selectivity in the reaction, while lowering temperature has a significant effect on the glycosylation outcome. The alpha/beta-ratio in the reaction with L-menthol as glycosyl acceptor was not affected by the molecular sieve pore size or NIS activator amount.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Ao Sun, Zipeng Li, Yuchao Wang, Shuai Meng, Xiao Zhang, Xiangbao Meng, Shuchun Li, Zhongtang Li, Zhongjun Li
Summary: This study presents an indirect method for the stereoselective synthesis of alpha-Kdo glycosides. The method utilizes a C3-p-tolylthio-substituted Kdo phosphite donor to achieve enhanced reactivity and complete alpha-stereocontrol. Various Kdo alpha-glycosides were successfully synthesized using this method. The orthogonality of the phosphite donor and thioglycoside donor was demonstrated through the one-pot synthesis of a trisaccharide. Furthermore, an efficient total synthesis route for a challenging 4,5-branched Kdo trisaccharide was highlighted. The high reactivity of the approach was further demonstrated by the synthesis of a highly crowded 4,5,7,8-branched Kdo pentasaccharide.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Kazuki Inaba, Yuna Naito, Mina Tachibana, Kazunobu Toshima, Daisuke Takahashi
Summary: A regioselective and beta-stereospecific d-/l-arabinofuranosylation method has been developed for efficient synthesis of biologically active natural glycosides. The method showed high regioselectivity and yield with complete beta-stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Frank F. J. de Kleijne, Hidde Elferink, Sam J. Moons, Paul B. White, Thomas J. Boltje
Summary: The study characterizes low-populated, rapidly equilibrating mannosyl dioxanium ions using chemical exchange saturation transfer (CEST) NMR spectroscopy, revealing their structure and equilibration kinetics under relevant glycosylation conditions. Highly alpha-selective couplings were observed, suggesting glycosylation takes place via this elusive intermediate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Zhen Wang, Ana Gimeno, Marta G. Lete, Herman S. Overkleeft, Gijsbert A. van der Marel, Fabrizio Chiodo, Jesus Jimenez-Barbero, Jeroen D. C. Codee
Summary: We report the first total synthesis of the Streptococcus pneumoniae serotype 1 (Sp1) oligosaccharide, which is a zwitterionic capsular polysaccharide carrying unstable O-acetyl esters. The synthesis was achieved by assembling trisaccharide building blocks in a highly stereoselective manner, up to the 9-mer level. The structure investigation revealed that the oligomers adopt a right-handed helical structure, with the acetyl esters exposed on the periphery and in close proximity of the neighboring AAT residues.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Medicinal
Samuel Boobier, Yufeng Liu, Krishna Sharma, David R. J. Hose, A. John Blacker, Nikil Kapur, Bao N. Nguyen
Summary: The study successfully utilized machine learning to predict the nucleophilicity parameter N in different solvents, demonstrating the effectiveness of the Causal Structure Property Relationship approach.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2021)
Article
Chemistry, Organic
Bryant Pero, Mark W. Peczuh
Summary: A new synthesis of carbohydrate-based oxepines using 2,3;4,6-di-O-acetonide mannose as a key starting material is reported. The oxepine is an important precursor used in the synthesis of septanose glycomimetics of mannopyranosides.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Polina I. Abronina, Nelly N. Malysheva, Alexander I. Zinin, Natalya G. Kolotyrkina, Leonid O. Kononov
Summary: Glycosylation using different glucosyl donors can lead to different selectivity, with the position of the benzoyl group playing a key role in the alpha selectivity.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Food Science & Technology
Lianghui Cheng, Renate Akkerman, Chunli Kong, Marthe T. C. Walvoort, Paul de Vos
Summary: Human milk is essential for newborn infants as it provides bioactive components like human milk oligosaccharides (hMOs) which have beneficial functions such as supporting growth of beneficial bacteria, anti-pathogenic effects, immune modulation, and stimulation of intestine barrier functions. The application of hMOs produced via genetically engineered microorganisms in infant formulas is a promising advancement in mimicking the nutritional composition of breast milk and overcoming scientific challenges.
CRITICAL REVIEWS IN FOOD SCIENCE AND NUTRITION
(2021)
Article
Chemistry, Applied
Michela Ferrari, Lisanne Hameleers, Marc C. A. Stuart, Marjolein M. P. Oerlemans, Paul de Vos, Edita Jurak, Marthe T. C. Walvoort
Summary: Bifidobacteria have many health benefits, and their exopolysaccharides (EPS) play an important role in these effects. However, the lack of knowledge about EPS localization has hindered their thorough investigation. This study presents a straightforward isolation procedure for obtaining EPS from four commercial bifidobacterial strains and demonstrates structural differences in the EPS, highlighting their potential for determining specific structure-activity effects.
CARBOHYDRATE POLYMERS
(2022)
Article
Multidisciplinary Sciences
Florian Leonardus Rudolfus Lucas, Roderick Corstiaan Abraham Versloot, Liubov Yakovlieva, Marthe T. C. Walvoort, Giovanni Maglia
Summary: Nanopores can be used for protein identification by measuring peptide spectra produced from hydrolyzed proteins. The spectra from nanopore experiments and mass spectrometry share similar profiles, enabling protein fingerprinting. This approach is quantitative, showing the potential of a low-cost, portable nanopore-based analyzer for protein identification.
NATURE COMMUNICATIONS
(2021)
Correction
Microbiology
Liubov Yakovlieva, Julius A. Fuelleborn, Marthe T. C. Walvoort
FRONTIERS IN MICROBIOLOGY
(2021)
Review
Microbiology
Liubov Yakovlieva, Julius A. Fuelleborn, Marthe T. C. Walvoort
Summary: Glycosylation, a universal process in nature, plays diverse roles in cells with various products like polysaccharides, glycoproteins, and glycolipids. Bacterial glycosylation systems, featuring unique characteristics, hold promise as potential antibacterial targets in research.
FRONTIERS IN MICROBIOLOGY
(2021)
Article
Oncology
V. C. Leeuwenburgh, C. G. Urzua-Traslavina, A. Bhattacharya, M. T. C. Walvoort, M. Jalving, S. de Jong, R. S. N. Fehrmann
Summary: By utilizing consensus independent component analyses on patient-derived tumor biopsies, this study identified 555 robust metabolic transcription components and demonstrated how they can be used to explore associations with drug sensitivities, patient outcomes, and the immune tumor microenvironment. The findings provide a valuable resource for formulating new hypotheses on metabolically engaging tumors or their microenvironments.
CANCER & METABOLISM
(2021)
Article
Chemistry, Organic
Niels R. M. Reintjens, Liubov Yakovlieva, Nittert Marinus, Johan Hekelaar, Francesca Nuti, Anna Maria Papini, Martin D. Witte, Adriaan J. Minnaard, Marthe T. C. Walvoort
Summary: Selective modification of carbohydrate residues in glycopeptides is important in glycobiology. In this study, palladium-catalyzed oxidation was used to achieve the same purpose, and the catalyst proved suitable for the oxidation of glucose residues. Careful optimization of reaction conditions is necessary to achieve desired conversion rates and avoid excessive oxidation of amino acid side-chains. The resulting carbonyl function can be used for oxime-ligation with biotin.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Roderick Corstiaan Abraham Versloot, Florian Leonardus Rudolfus Lucas, Liubov Yakovlieva, Matthijs Jonathan Tadema, Yurui Zhang, Thomas M. Wood, Nathaniel I. Martin, Siewert J. Marrink, Marthe T. C. Walvoort, Giovanni Maglia
Summary: This study demonstrates the ability to detect and quantify posttranslational modifications in proteins using nanopores by adjusting ionic strength, pH, and using specific nanopores. This addresses one of the pressing challenges in proteomic analysis.
Article
Multidisciplinary Sciences
Andreea A. Gheorghita, Yancheng E. Li, Elena N. Kitova, Duong T. Bui, Roland Pfoh, Kristin E. Low, Gregory B. Whitfield, Marthe T. C. Walvoort, Qingju Zhang, Jeroen D. C. Codee, John S. Klassen, P. Lynne Howell
Summary: This study reveals the molecular mechanism of synthase-dependent secretion systems in producing exopolysaccharides, providing insights into the role of Pseudomonas aeruginosa in lung infections.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Applied
Pushpa Rampratap, Alessia Lasorsa, Barbara Perrone, Patrick C. A. van der Wel, Marthe T. C. Walvoort
Summary: Hyaluronic acid (HA), a polysaccharide in the extracellular matrix (ECM) of vertebrate cells, is being widely studied for its applications in hydrogels due to its high viscoelasticity and biocompatibility. However, there are limited techniques available to understand the structural and functional properties of HA-containing hydrogels. In this study, a convenient method to obtain enriched high molecular weight (HMW)-HA labeled with 13C and 15N is presented, which allows for advanced NMR techniques to study the structure and dynamics of HMW-HA-based hydrogels and their interactions with proteins and other ECM components.
CARBOHYDRATE POLYMERS
(2023)
Article
Biochemistry & Molecular Biology
Kristin E. Low, Andreea A. Gheorghita, Stephanie D. Tammam, Gregory B. Whitfield, Yancheng E. Li, Laura M. Riley, Joel T. Weadge, Shane J. Caldwell, P. Andrew Chong, Marthe T. C. Walvoort, Elena N. Kitova, John S. Klassen, Jeroen D. C. Codee, P. Lynne Howell
Summary: Enzymatic modifications of bacterial exopolysaccharides enhance immune evasion and persistence during infection. In this study, the researchers investigate the role of AlgF protein in coordinating the modification of alginate in Pseudomonas aeruginosa. They identify its interactions with other proteins and propose that AlgF mediates protein-protein interactions to form a complex necessary for biofilm formation.
JOURNAL OF BIOLOGICAL CHEMISTRY
(2023)
Article
Chemistry, Organic
Niels R. M. Reintjens, Imke M. A. Bartels, Nittert Marinus, Sarina C. Massmann, Daan V. Bunt, Marthe T. C. Walvoort, Martin D. Witte, Adriaan J. Minnaard
Summary: This study reports a simplified protocol for the selective oxidation of unprotected carbohydrates using a palladium catalyst. The reaction protocol offers a more convenient method with simplified steps and product isolation, and can be applied to a variety of sugar compounds.
Article
Biochemistry & Molecular Biology
Xin Tang, Martin Beukema, Michela Ferrari, Marthe T. C. Walvoort, Bart J. J. de Haan, Paul de Vos
Summary: Pectins play a role in supporting intestinal barrier function and have anti-diabetic effects, and the degree of methyl-esterification (DM) and distribution of non-esterified galacturonic acid residues (DB) may differ in pectins. The mechanisms and effects of pectin type at different glucose levels are unknown.
Article
Biochemistry & Molecular Biology
Stella A. Verkhnyatskaya, Chunli Kong, Cynthia E. Klostermann, Henk A. Schols, Paul de Vos, Marthe T. C. Walvoort
Summary: The novel compound di-fucosyl-beta-cyclodextrin (DF beta CD), inspired by the molecular structures of hMOs, shows potential in digestion, fermentation, and anti-adhesive capacity, particularly against certain pathogenic bacteria.
Article
Chemistry, Multidisciplinary
Liubov Yakovlieva, Thomas M. Wood, Johan Kemmink, Ioli Kotsogianni, Franziska Koller, Juergen Lassak, Nathaniel I. Martin, Marthe T. C. Walvoort
Summary: The bacterial enzyme EarP recognizes a beta-hairpin loop when transferring rhamnose to a specific arginine residue. Its activity is sensitive to the method used for inducing cyclization and shows some tolerance to amino acid sequence variation.
