Structure, network density and domain architecture of transition-metal (Cu2+, Fe3+) cross-linked alginates as seen by paramagnetic solid-state NMR spectroscopy

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61389013%3A_____%2F25%3A00639379" target="_blank" >RIV/61389013:_____/25:00639379 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216224:14160/25:00142068

Výsledek na webu

<a href="https://www.sciencedirect.com/science/article/pii/S014486172501152X?via%3Dihub" target="_blank" >https://www.sciencedirect.com/science/article/pii/S014486172501152X?via%3Dihub</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.carbpol.2025.124367" target="_blank" >10.1016/j.carbpol.2025.124367</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Structure, network density and domain architecture of transition-metal (Cu2+, Fe3+) cross-linked alginates as seen by paramagnetic solid-state NMR spectroscopy

Popis výsledku v původním jazyce

Owing to the regenerative nature of metal-coordination bonds, transition metal-crosslinked alginates are of increasing technological relevance. However, due to their amorphous character and paramagnetic nature, their atomic-resolution structure, which is crucial for optimizing physicochemical properties, has long remained elusive. By employing very fast (VF) magic angle spinning (MAS) nuclear magnetic resonance (NMR) we overcame experimental challenges and obtained previously unreported data on the structure, network density, and domain architecture of alginates crosslinked by paramagnetic Cu2+ and Fe3+ ions, and modified by lactic acid - a pharmaceutically relevant ingredient that alters pH and crosslinking mechanism. We identified a high proportion of carboxyl units COOH coexisting with deprotonated carboxylate COO− groups, nanoscale acidic domains, and strongly hyperfine-coupled nuclei within the paramagnetic matrix, revealing the specific coordination geometry of the Cu2+ and Fe3+ ions utilizing hydroxyl groups. These results provide new insight into the structural complexity of amorphous paramagnetic biopolymers and demonstrate the analytical power of VF/MAS NMR in challenging environments. The present research thus aims to provide one of the first experimentally confirmed representations of the complex interactions in alginates crosslinked with paramagnetic transition metal ions. These findings have direct implications for the synthesis of novel functional materials based on carbohydrate polymers.

Název v anglickém jazyce

Structure, network density and domain architecture of transition-metal (Cu2+, Fe3+) cross-linked alginates as seen by paramagnetic solid-state NMR spectroscopy

Popis výsledku anglicky

Owing to the regenerative nature of metal-coordination bonds, transition metal-crosslinked alginates are of increasing technological relevance. However, due to their amorphous character and paramagnetic nature, their atomic-resolution structure, which is crucial for optimizing physicochemical properties, has long remained elusive. By employing very fast (VF) magic angle spinning (MAS) nuclear magnetic resonance (NMR) we overcame experimental challenges and obtained previously unreported data on the structure, network density, and domain architecture of alginates crosslinked by paramagnetic Cu2+ and Fe3+ ions, and modified by lactic acid - a pharmaceutically relevant ingredient that alters pH and crosslinking mechanism. We identified a high proportion of carboxyl units COOH coexisting with deprotonated carboxylate COO− groups, nanoscale acidic domains, and strongly hyperfine-coupled nuclei within the paramagnetic matrix, revealing the specific coordination geometry of the Cu2+ and Fe3+ ions utilizing hydroxyl groups. These results provide new insight into the structural complexity of amorphous paramagnetic biopolymers and demonstrate the analytical power of VF/MAS NMR in challenging environments. The present research thus aims to provide one of the first experimentally confirmed representations of the complex interactions in alginates crosslinked with paramagnetic transition metal ions. These findings have direct implications for the synthesis of novel functional materials based on carbohydrate polymers.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10404 - Polymer science

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Carbohydrate Polymers

ISSN

0144-8617

e-ISSN

1879-1344

Svazek periodika

370

Číslo periodika v rámci svazku

15 December

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

14

Strana od-do

124367

Kód UT WoS článku

001576870600004

EID výsledku v databázi Scopus

2-s2.0-105015960300