Article
Biochemistry & Molecular Biology
Sergey P. Babailov, Eugeny N. Zapolotsky, Eduard S. Fomin, Marina A. Polovkova, Gayane A. Kirakosyan, Alexander G. Martynov, Yulia G. Gorbunova
Summary: The detailed knowledge of the structure of multinuclear paramagnetic lanthanide complexes is crucial for designing compounds with special properties. However, determining the structure of these complexes in solution using NMR is challenging due to the simultaneous effect of multiple paramagnetic centers on the chemical shift. In this study, the possibility of determining the molecular structure in solution was demonstrated using quantitative analysis of pseudo-contact lanthanide-induced shifts (LIS) in binuclear triple-decker lanthanide(III) complexes. The symmetry of the complexes simplified the calculation of pseudo-contact shifts and the good agreement between calculated and experimental shifts confirmed the similarity of the structures in solution and the crystalline phase.
Article
Chemistry, Multidisciplinary
Marta G. Lete, Antonio Franconetti, Sara Bertuzzi, Sandra Delgado, Mikel Azkargorta, Felix Elortza, Oscar Millet, Gonzalo Jimenez-Oses, Ana Arda, Jesus Jimenez-Barbero
Summary: Fluorine (F-19) incorporation into lectins has allowed monitoring of carbohydrate binding through NMR spectroscopy. Galectin-3 (Gal3) and Galectin-8 (Gal8) with one and two carbohydrate recognition domains (CRDs), respectively, were chosen. The presence of fluorine did not significantly affect glycan binding affinity, and allowed differentiation of binding events at different sites within the same lectin.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Biochemistry & Molecular Biology
Rosa Ester Forgione, Ferran Fabregat Nieto, Cristina Di Carluccio, Francesco Milanesi, Martina Fruscella, Francesco Papi, Cristina Nativi, Antonio Molinaro, Pasquale Palladino, Simona Scarano, Maria Minunni, Marco Montefiori, Monica Civera, Sara Sattin, Oscar Francesconi, Roberta Marchetti, Alba Silipo
Summary: In this study, two conformationally constrained sialyl analogues were synthesized and characterized for their interaction with human CD22 protein. The results demonstrate the potential of these analogues as novel CD22 inhibitors and provide new insights for modifying and synthesizing sialic acid. Furthermore, they offer promising prospects for therapeutic intervention in autoimmune diseases and B-cell malignancies.
Article
Chemistry, Multidisciplinary
Irene Herrera-Gonzalez, Michel Thepaut, Elena M. Sanchez-Fernandez, Antonio di Maio, Corinne Vives, Javier Rojo, Jose M. Garcia Fernandez, Franck Fieschi, Pedro M. Nieto, Carmen Ortiz Mellet
Summary: Selective targeting of DC-SIGN and langerin may lead to the development of anti-infective agents. This study demonstrates that multivalent sp(2)-iminosugar-containing mannobioside analogs can achieve total DC-SIGN selectivity by leveraging the canonical binding mode towards high-mannose oligosaccharide ligands, acting as real biomimics.
CHEMICAL COMMUNICATIONS
(2022)
Review
Biochemistry & Molecular Biology
Francisco Javier Canada, Angeles Canales, Pablo Valverde, Beatriz Fernandez de Toro, Monica Martinez-Orts, Paola Oquist Phillips, Amaia Pereda
Summary: Carbohydrates, either as free molecules or conjugated with other biomolecules, play important roles in various biological processes. Nuclear Magnetic Resonance spectroscopy (NMR) is a versatile tool for studying the structures and interactions of carbohydrates, providing information about their sequences, structures, and local geometries. Labeling carbohydrates with 13C enhances the resolution and detail of the analyzed structures. Moreover, combining NMR with molecular modeling and theoretical calculations offers insights into the conformational flexibility of carbohydrates. Additionally, the use of partially oriented media or paramagnetic perturbations allows for the study of longer and branched glycan chains. This review presents examples and an overview of recent and relevant NMR applications in the field of glycobiology.
CURRENT MEDICINAL CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Anna Notaro, Yohann Coute, Lucid Belmudes, Maria Elena Laugeri, Annalisa Salis, Gianluca Damonte, Antonio Molinaro, Michela G. Tonetti, Chantal Abergel, Cristina De Castro
Summary: The traditional perception of viruses being small and hijacking host machinery for glycosylation is challenged by the discovery of giant viruses with complex genomes and unique polysaccharide glycocalyces. These findings blur the boundaries between giant viruses and the cellular world, opening new avenues in the field of viral glycobiology.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Takaya Fujie, Takeshi Yamamoto, Michinori Suginome
Summary: A single-handed poly(quinoxaline-2,3-diyl) (PQX) has been discovered as a new type of chiral shift reagent (CSR) for determining enantiomeric ratio by NMR spectroscopy. Without specific binding site, PQX interacts nonbondingly with chiral analytes, resulting in significant shift of NMR chemical shift and enabling quantification of enantiomeric ratios. This new CSR offers advantages such as wide analyte scope, including ethers, haloalkanes, and alkanes, easy tunability of chemical shifts with temperature, and erasability of proton signals due to short T-2 relaxation of the macromolecular scaffold.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Ana Garcia-Garcia, Sonia Serna, Zhang Yang, Ignacio Delso, Victor Taleb, Thomas Hicks, Raik Artschwager, Sergey Y. Vakhrushev, Henrik Clausen, Jesus Angulo, Francisco Corzana, Niels C. Reichardt, Ramon Hurtado-Guerrero
Summary: Core fucosylation by FUT8 is affected by the underlying peptide sequence for paucimannose and high-mannose N-glycans, but not for complex-type N-glycans. FUT8 recognizes all sugar units and most amino acid residues of the G0 N-glycan, with optimal recognition requiring prior binding to GDP-Fuc. Genetic engineering in CHO cells demonstrated that core fucosylation mainly occurs on complex-type N-glycans, but certain glycosites can acquire Fuc on high-mannose N-glycans.
Article
Chemistry, Multidisciplinary
Min Lin, Jingfang Xiong, Mintao Su, Feng Wang, Xiangsi Liu, Yifan Hou, Riqiang Fu, Yong Yang, Jun Cheng
Summary: This article introduces a new machine learning protocol for the application of solid-state nuclear magnetic resonance (ssNMR) in high-rate battery materials, and successfully validates the significance of the protocol.
Article
Biochemistry & Molecular Biology
Anna Harari, Guy Zoltsman, Tal Levin, Rina Rosenzweig
Summary: This study structurally characterizes the interaction between Hsp104 NTD and substrates by using NMR spectroscopy. The NTD has a substrate-binding groove that specifically recognizes exposed hydrophobic stretches in Hsp104 substrates. The NTD itself also has chaperoning activities to protect the substrates from further misfolding and aggregation.
Article
Chemistry, Physical
Janet Muzulu, Amit Basu
Summary: STD NMR spectroscopy was used to observe the interaction between phenylboronic acids and synthetic glycopolymers, generating an epitope map for the bound boronic acids. Additionally, STD NMR detected the interaction between indole and a galactosylated glycopolymer, providing insights into the CH-pi interaction in carbohydrate recognition.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Luca Unione, Maria J. Moure, Maria Pia Lenza, Iker Oyenarte, June Ereno-Orbea, Ana Arda, Jesus Jimenez-Barbero
Summary: The interaction between the SARS CoV2 spike glycoprotein and two sialic acid-containing trisaccharides has been demonstrated, with the sialic acid binding site located at the N-terminal domain.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Sara Bertuzzi, Francesca Peccati, Sonia Serna, Raik Artschwager, Simona Notova, Michel Thepaut, Gonzalo Jimenez-Oses, Franck Fieschi, Niels C. Reichardt, Jesus Jimenez-Barbero, Ana Arda
Summary: The molecular recognition features of LSECtin towards asymmetric N-glycans were scrutinized by NMR and compared to glycan microarrays. It was found that both asymmetric LDN3 and LDN6 N-glycans are recognized by LSECtin with similar affinities in solution, contrary to the results obtained on microarrays, where only LDN6 was efficiently recognized by the lectin.
ACS CENTRAL SCIENCE
(2022)
Article
Engineering, Electrical & Electronic
Sergey P. Babailov, Marina A. Polovkova, Gayane A. Kirakosyan, Alexander G. Martynov, Evgeny N. Zapolotsky, Yulia G. Gorbunova
Summary: This paper demonstrates the thermosensing properties of binuclear triple-decker terbium(III) and dysprosium(III) complexes at physiological temperature range, with terbium-containing complex showing the highest sensitivity among published complexes in nonpolar solutions. The significant impact of Curie-spin contribution on paramagnetic spin-spin relaxation rate enhancement with pronounced temperature dependence is also highlighted.
SENSORS AND ACTUATORS A-PHYSICAL
(2021)
Article
Chemistry, Organic
Ning Xi, Mingming Sun, Yang Lu, Changlin Bai
Summary: Covalently identical ortho-F nuclei display dual 19F NMR signals in di-ortho-F substituted N-phenyl glactams. Structural variations at C9-substituent on the g-lactam lead to larger chemical shift changes at downfield 19F signals (ddown) than those at upfield 19F signals (dup). A reverse correlation between downfield 19F chemical shifts and electron-withdrawing abilities of C9-phenylamides is observed. Electrostatic effects are the major forces between C9-substituents and ortho-F nuclei, and Hammett parameters can be used to describe such through-space interactions. Structural factors influencing ortho-19F shielding among diverse C9-substituted N-phenyl g-lactams are discussed.
Article
Chemistry, Multidisciplinary
Francesco Milanesi, Luca Unione, Ana Arda, Cristina Nativi, Jesus Jimenez-Barbero, Stefano Roelens, Oscar Francesconi
Summary: Glycomics research has revealed the essential role of carbohydrates in biological systems and the importance of chemical tools in studying glycan function. While biomimetic receptors can selectively bind to simple saccharides, this study demonstrates the unprecedented recognition of a complex glycopeptide by a biomimetic receptor. The receptor shows high affinity for the core disaccharide of the N-glycan and has the potential for versatile applications in glycoscience.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Marta G. Lete, Antonio Franconetti, Sara Bertuzzi, Sandra Delgado, Mikel Azkargorta, Felix Elortza, Oscar Millet, Gonzalo Jimenez-Oses, Ana Arda, Jesus Jimenez-Barbero
Summary: Fluorine (F-19) incorporation into lectins has allowed monitoring of carbohydrate binding through NMR spectroscopy. Galectin-3 (Gal3) and Galectin-8 (Gal8) with one and two carbohydrate recognition domains (CRDs), respectively, were chosen. The presence of fluorine did not significantly affect glycan binding affinity, and allowed differentiation of binding events at different sites within the same lectin.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Biochemistry & Molecular Biology
Ana Pozo-Rodriguez, Juan A. A. Mendez-Liter, Rocio Garcia-Villalba, David Beltran, Eva Calvino, Andres G. Santana, Laura I. I. De Eugenio, Francisco Javier Canada, Alicia Prieto, Jorge Barriuso, Francisco A. A. Tomas-Barberan, Maria Jesus Martinez
Summary: Resveratrol was glycosylated by using rXynSOS-E236G glycosynthase, resulting in the production of 3-O-beta-D-xylobiosyl resveratrol as the major product. Response surface methodology was used to optimize the reaction, yielding 35% of 3-O-beta-D-xylobiosyl resveratrol. Xylobiosylation decreased the antioxidant capacity of resveratrol, but significantly improved its solubility for improved delivery and transit to the colon.
Article
Nanoscience & Nanotechnology
Anna Blasi-Romero, Molly Angstrom, Antonio Franconetti, Taj Muhammad, Jesus Jimenez-Barbero, Ulf Goransson, Carlos Palo-Nieto, Natalia Ferraz
Summary: This study combines the wound-healing properties of KR-12 peptide with wood-derived cellulose nanofibrils (CNFs) to create bioactive materials for treating chronic wounds. Different coupling chemistries were used to covalently attach KR-12 derivatives onto CNFs, and the bioactivity of KR12-CNF conjugates was evaluated in terms of antibacterial activities and anti-inflammatory effects. The results showed that thiol-ene chemistry produced the most bioactive conjugates, attributed to favorable peptide conformation and accessibility. This study advances the development of CNF-based materials for chronic wound care and provides insights into the effect of conjugation chemistry on the bioactivity of host defense peptides.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Alvaro Mallagaray, Lorena Rudolph, Melissa Lindloge, Jarne Moelbitz, Henrik Thomsen, Franziska Schmelter, Mohamad Ward Alhabash, Mohammed R. Abdullah, Roza Saraei, Marc Ehlers, Tobias Graf, Christian Sina, Astrid Petersmann, Matthias Nauck, Ulrich L. Guenther
Summary: Nuclear Magnetic Resonance (NMR) spectra of human serum and plasma can identify the signals GlycA and GlycB, which come from the acetyl groups of glycoprotein glycans and serve as markers for inflammatory processes. This study provides a detailed assignment of glycoprotein glycan NMR signals in human serum, revealing that GlycA and GlycB signals correspond to specific N-glycans. The concentrations of acute phase glycoproteins, determined conventionally, show a strong correlation with distinctive features in the NMR spectra, enabling the simultaneous quantification of multiple acute phase inflammation proteins.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Zhen Wang, Ana Poveda, Qingju Zhang, Luca Unione, Herman S. Overkleeft, Gijsbert A. van der Marel, Jimenez-Barbero Jesus, Jeroen D. C. Codee
Summary: Researchers have successfully synthesized a series of polysaccharide fragments with a unique structure that can activate T cells and bind to specific receptors. Detailed structural studies have revealed the secondary structure of these fragments, providing a basis for further understanding their mode of action.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Matteo A. . Tallarida, Fabrizio Olivito, Claudio D. Navo, Vincenzo Algieri, Antonio Jiritano, Paola Costanzo, Ana Poveda, Maria J. Moure, Jesus Jimenez-Barbero, Loredana Maiuolo, Gonzalo Jimenez-Oses, Antonio De Nino
Summary: The synthesis of polysubstituted spirocyclopropyl oxindoles using rare-earth metal (REM) salts, particularly Sc(OTf)3, was achieved with high diastereoselectivity (<= 94:6:0:0) in a multicomponent reaction. Density functional theory calculations on the model reaction confirmed the observed selectivity and demonstrated that the coordinating capabilities and oxophilicity of the metal played a crucial role in inducing the formation of one main diastereoisomer.
Article
Biochemistry & Molecular Biology
Hans-Christian Siebert, Thomas Eckert, Anirban Bhunia, Nele Klatte, Marzieh Mohri, Simone Siebert, Anna Kozarova, John W. Hudson, Ruiyan Zhang, Ning Zhang, Lan Li, Konstantinos Gousias, Dimitrios Kanakis, Mingdi Yan, Jesus Jimenez-Barbero, Tibor Kozar, Nikolay E. Nifantiev, Christian Vollmer, Timo Brandenburger, Detlef Kindgen-Milles, Thomas Haak, Athanasios K. Petridis
Summary: The global outbreak of SARS-CoV-2/COVID-19 has provided an opportunity and challenge to accumulate a large amount of biomedical data and test new concepts and strategies to combat the pandemic. This study correlated clinical biomedical data with structural biology and biophysical data to evaluate new diagnostic and therapeutic approaches against SARS-CoV-2. The methods used were effective in identifying potential peptide sequences and carbohydrate moieties to protect the blood-brain barrier and develop new therapeutic approaches against long-COVID symptoms.
Article
Chemistry, Multidisciplinary
Angeles Canales, Javier Sastre, Jose M. Orduna, Cindy M. Spruit, Javier Perez-Castells, Gema Dominguez, Kim M. Bouwman, Roosmarijn van der Woude, Francisco Javier Canada, Corwin M. Nycholat, James C. Paulson, Geert-Jan Boons, Jesus Jimenez-Barbero, Robert P. de Vries
Summary: Influenza virus infection remains a threat to human health due to the drifting of viral hemagglutinins, which evade infection and vaccine-induced antibody responses. Recent H3N2 and pandemic H1 viruses specifically recognize glycan structures containing at least three N-acetyllactosamine units. This study characterizes the glycan specificity of H1 variants, including the one responsible for the 2009 pandemic outbreak, and investigates the preference for tri-LacNAc motifs in human-type receptor-adapted viruses using glycan arrays, tissue binding analyses, and nuclear magnetic resonance experiments.
Article
Biophysics
Fernando Pradanas-Gonzales, Riikka Peltomaa, Satu Lahtinen, Alvaro Luque-Uria, Vicente Mas, Rodrigo Barderas, Chris M. Maragos, Angeles Canales, Tero Soukka, Elena Benito-Pena, Maria C. Moreno-Bondi
Summary: A homogeneous upconversion-resonance energy transfer (UC-RET) immunoassay was developed for the detection of the neurotoxin a-cyclopiazonic acid (CPA). The assay showed high sensitivity and specificity for CPA and was applied to detect CPA in maize samples.
BIOSENSORS & BIOELECTRONICS
(2023)
Article
Chemistry, Multidisciplinary
Giulio Fittolani, Theodore Tyrikos-Ergas, Ana Poveda, Yang Yu, Nishu Yadav, Peter H. Seeberger, Jesus Jimenez-Barbero, Martina Delbianco
Summary: This article introduces a synthetic glycan molecule that adopts a stable secondary structure not found in nature, called a glycan hairpin. The synthetic glycan is created by combining natural glycan motifs and utilizing unconventional hydrogen bonds and hydrophobic interactions. Nuclear magnetic resonance conformational analysis and long-range inter-residue nuclear Overhauser effects confirm the folded conformation of the synthetic glycan hairpin. The ability to control the 3D shape of glycans has the potential to provide more foldamer scaffolds with programmable properties and functions.
Article
Immunology
Leticia Martin-Cruz, Marcos Vinuela, Ioanna Kalograiaki, Alba Angelina, Paola Oquist-Phillips, Irene Real-Arevalo, Francisco Javier Canada, Jose Ignacio Tudela, Luis Molto, Jesus Moreno-Sierra, Jose Luis Subiza, Oscar Palomares
Summary: This study reveals novel molecular mechanisms by which heparan sulfate-related structures associated with tumor cells promote the generation of functional Tregs in cancer. Furthermore, the presence of a circulating human Ca10 counterpart (Ca10H) in cancer patients and its correlation with tumor size and metastasis suggests important clinical implications in cancer treatment.
CELLULAR & MOLECULAR IMMUNOLOGY
(2023)
Article
Neurosciences
Irene B. Maroto, Estefania Moreno, Carlos Costas-Insua, Javier Merino-Gracia, Rebeca Diez-Alarcia, Alicia Alvaro-Blazquez, Angeles Canales, Enric I. Canela, Vicent Casado, Leyre Uriguen, Ignacio Rodriguez-Crespo, Manuel Guzman
Summary: Cannabinoids have pleiotropic effects on the brain by interacting with the CB1 receptor. This study reveals that the interaction between CB1 receptor and GAP43 modulates CB1 receptor signaling in a highly selective manner, specifically impairing the ROCK signaling pathway and controlling neurite outgrowth.
