Balancing Chemical and Supramolecular Stability in OEGylated Supramolecular Polymers for Systemic Drug Delivery DOI
Weijie Zhang, Feihu Wang, Han Wang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 15, 2025

The chemical conjugation of poly(ethylene glycol) (PEG) to therapeutic agents, known as PEGylation, is a well-established strategy for enhancing drug solubility, stability, and pharmacokinetics. Here, we report on class supramolecular polymeric prodrugs by utilizing oligo(ethylene (OEG) modify the hydrophobic anticancer camptothecin (CPT). These OEGylated prodrugs, despite their low molecular weight, spontaneously self-assemble into polymers (SPs) with tubular morphology, featuring dense OEG coating surface. By designing biodegradable linkers varying stabilities, investigated how release kinetics CPT influence in vitro vivo performance these SPs. Our findings demonstrate that self-assembling (SAPDs) self-immolative disulfanyl-ethyl carbonate (etcSS) linker exhibit faster rate than those reducible disulfanyl butyrate (buSS) linker, leading higher potency significantly improved antitumor efficacy. Notably, two stable SPs, Tubustecan (TT) 1E TT 7E, outperformed irinotecan─a clinically approved prodrug─in colon cancer model, achieving enhanced tumor growth inhibition prolonged animal survival. results highlight potential OEGylation an important engineering drug-based underscore critical role stability vs optimizing prodrug design.

Language: Английский

A Collagen Triple Helix without the Superhelical Twist DOI Creative Commons
Mark A. B. Kreutzberger, Le Yu, Thi H. Bui

et al.

ACS Central Science, Journal Year: 2025, Volume and Issue: 11(2), P. 331 - 345

Published: Feb. 4, 2025

Collagens are ubiquitous in biology: functioning as the backbone of extracellular matrix, forming primary structural components key immune system complexes, and fulfilling numerous other roles a variety systems. Despite this, there is limited understanding how triple helices, basic collagen units, pack into collagenous assemblies. Here we use peptide self-assembly to design assemblies based on C1q collagen-like region. Using cryo-EM solved structure one assembly 3.5 Å resolution built an atomic model. From identify helix conformation with no superhelical twist, starkly contrast canonical right-handed helix. This nontwisting region allows for unique hydroxyproline stacking between adjacent helices also results formation exposed cavity rings hydrophobic amino acids packed symmetrically. We find precedent such arrangement designed substituted various locations probe stabilizing acid interactions complex. The stability these altered complexes behaves predicted by our Our findings, combined extremely experimental data packing literature, suggest that may adopt far more varied conformational landscape than previously appreciated. hypothesize this particularly likely termini at discontinuities required Xaa-Yaa-Gly repeating sequence, discontinuity found majority class proteins many collagen-associated diseases.

Language: Английский

Citations

0

Supramolecular assembly of collagen mimetic peptide D-periodic fibrils and nanoassemblies DOI Creative Commons
Carson C. Cole, Mark A. B. Kreutzberger, K. Klein

et al.

bioRxiv (Cold Spring Harbor Laboratory), Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 16, 2025

Abstract The collagen triple helix assembles hierarchically into bundled oligomers, solvated networks and fibers. Synthetic peptide assemblies, driven by supramolecular interactions, can form single helices through intrahelical amino acid pairs, but the principles guiding interhelical associations higher-order structures remain unclear. Here, we incorporate cation- π electrostatic charge pairs to probe interactions elucidate mechanisms driving assembly fibrils, nanotubes, nanosheets. Introducing a fibrillating mimetic resulted in D-periodic fibrils with pH-sensitive gelation. Modifying presentation of also enabled characterization another fibril resembling cartilage collagens, featuring inner outer layers. Enhancing promoted antiparallel assembly, leading formation nanotubes packing behavior correlates where parallel favor formation, drive nanotube nanosheet assembly.

Language: Английский

Citations

0

Hierarchical Assemblies of Collagen-Mimetic Peptides: From a Fundamental Understanding to Developing Biomaterials DOI
Debajit Kalita, Bani Kanta Sarma

Langmuir, Journal Year: 2025, Volume and Issue: unknown

Published: April 4, 2025

Collagen is the most abundant protein in animals and crucial for maintaining structural functional integrity of extracellular matrix. Its primary structure consists ∼300 repeats Xaa-Yaa-Gly triplet, where Xaa Yaa are often proline (Pro) 4-(R)-hydroxyproline (Hyp) residues, respectively. fundamentally a right-handed triple helix that undergoes self-association, forming complex supramolecular structures body. Despite extensive study, detailed mechanisms behind its higher-order assembly remain unclear due to challenges purification post-translational modifications it undergoes. To better understand molecular aspects collagen's structure, researchers developed collagen-mimetic peptides (CMPs)─short composed 7-17 triplets─easily synthesized laboratory. Over years, research on CMPs has provided significant insights into formation stability collagen helix. However, creating multihierarchical self-assembled beyond remains challenging. Recently, various strategies such as covalent linkages, salt-bridge interactions, incorporation hydrophobic groups, metal-coordinated assembly, coassembly with foreign partners have been employed design CMP assemblies. These innovations led creation fibers, 2D sheets, wires, spherical micelles. This progress paved way rational novel peptide-based biomaterials, which may offer advantages over animal-derived collagen, including absence potential allergens contaminants. review highlights recent advancements design, discussing principles, challenges, prospects these biomaterials clinical applications.

Language: Английский

Citations

0

Balancing Chemical and Supramolecular Stability in OEGylated Supramolecular Polymers for Systemic Drug Delivery DOI
Weijie Zhang, Feihu Wang, Han Wang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 15, 2025

The chemical conjugation of poly(ethylene glycol) (PEG) to therapeutic agents, known as PEGylation, is a well-established strategy for enhancing drug solubility, stability, and pharmacokinetics. Here, we report on class supramolecular polymeric prodrugs by utilizing oligo(ethylene (OEG) modify the hydrophobic anticancer camptothecin (CPT). These OEGylated prodrugs, despite their low molecular weight, spontaneously self-assemble into polymers (SPs) with tubular morphology, featuring dense OEG coating surface. By designing biodegradable linkers varying stabilities, investigated how release kinetics CPT influence in vitro vivo performance these SPs. Our findings demonstrate that self-assembling (SAPDs) self-immolative disulfanyl-ethyl carbonate (etcSS) linker exhibit faster rate than those reducible disulfanyl butyrate (buSS) linker, leading higher potency significantly improved antitumor efficacy. Notably, two stable SPs, Tubustecan (TT) 1E TT 7E, outperformed irinotecan─a clinically approved prodrug─in colon cancer model, achieving enhanced tumor growth inhibition prolonged animal survival. results highlight potential OEGylation an important engineering drug-based underscore critical role stability vs optimizing prodrug design.

Language: Английский

Citations

0