Matrix Metalloproteinase-2-Responsive Peptide-Modified Cleavable PEGylated Liposomes for Paclitaxel Delivery

<b>Background/Objectives</b>: PEGylated liposomes are widely recognized for their biocompatibility and capacity to extend systemic circulation via “stealth” properties. However, the PEG corona often limits tumor penetration and cellular internalization. Targeting matrix metalloproteinase...

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Main Authors: Xingyu Zhao, Yinghuan Li
Format: Article
Language:English
Published: MDPI AG 2025-07-01
Series:Pharmaceuticals
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Online Access:https://www.mdpi.com/1424-8247/18/7/1042
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author Xingyu Zhao
Yinghuan Li
author_facet Xingyu Zhao
Yinghuan Li
author_sort Xingyu Zhao
collection DOAJ
description <b>Background/Objectives</b>: PEGylated liposomes are widely recognized for their biocompatibility and capacity to extend systemic circulation via “stealth” properties. However, the PEG corona often limits tumor penetration and cellular internalization. Targeting matrix metalloproteinase-2 (MMP-2), frequently upregulated in breast cancer stroma, presents an opportunity to enhance tissue-specific drug delivery. In this study, we engineered MMP-2-responsive GPLGVRG peptide-modified cleavable PEGylated liposomes for targeted paclitaxel (PTX) delivery. <b>Methods</b>: Molecular docking simulations employed the MMP-2 crystal structure (PDB ID: 7XJO) to assess GPLGVRG peptide binding affinity. A cleavable, enzyme-sensitive peptide-PEG conjugate (Chol-PEG<sub>2K</sub>-GPLGVRG-PEG<sub>5K</sub>) was synthesized via small-molecule liquid-phase synthesis and characterized by <sup>1</sup>H NMR and MALDI-TOF MS. Liposomes incorporating this conjugate (S-Peps-PEG<sub>5K</sub>) were formulated to evaluate whether MMP-2-mediated peptide degradation triggers detachment of long-chain PEG moieties, thereby enhancing internalization by 4T1 breast cancer cells. Additionally, the effects of tumor microenvironmental pH (~6.5) and MMP-2 concentration on drug release dynamics were investigated. <b>Results</b>: Molecular docking revealed robust GPLGVRG-MMP-2 interactions, yielding a binding energy of −7.1 kcal/mol. The peptide formed hydrogen bonds with MMP-2 residues Tyr A:23 and Arg A:53 (bond lengths: 2.4–2.5 Å) and engaged in hydrophobic contacts, confirming MMP-2 as the primary recognition site. Formulations containing 5 mol% Chol-PEG<sub>2K</sub>-GPLGVRG-PEG<sub>5K</sub> combined with 0.15 µg/mL MMP-2 (S-Peps-PEG<sub>5K</sub> +MMP) exhibited superior internalization efficiency and significantly reduced clonogenic survival compared to controls. Notably, acidic pH (~6.5) induced MMP-2-mediated cleavage of the GPLGVRG peptide, accelerating S-Peps-PEG<sub>5K</sub> dissociation and facilitating drug release. <b>Conclusions</b>: MMP-2-responsive, cleavable PEGylated liposomes markedly improve PTX accumulation and controlled release at tumor sites by dynamically modulating their stealth properties, offering a promising strategy to enhance chemotherapy efficacy in breast cancer.
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spelling doaj-art-fd4358e2e48a452db0a7198575b9389a2025-08-20T02:47:07ZengMDPI AGPharmaceuticals1424-82472025-07-01187104210.3390/ph18071042Matrix Metalloproteinase-2-Responsive Peptide-Modified Cleavable PEGylated Liposomes for Paclitaxel DeliveryXingyu Zhao0Yinghuan Li1School of Pharmaceutical Sciences, Capital Medical University, Beijing 100069, ChinaSchool of Pharmaceutical Sciences, Capital Medical University, Beijing 100069, China<b>Background/Objectives</b>: PEGylated liposomes are widely recognized for their biocompatibility and capacity to extend systemic circulation via “stealth” properties. However, the PEG corona often limits tumor penetration and cellular internalization. Targeting matrix metalloproteinase-2 (MMP-2), frequently upregulated in breast cancer stroma, presents an opportunity to enhance tissue-specific drug delivery. In this study, we engineered MMP-2-responsive GPLGVRG peptide-modified cleavable PEGylated liposomes for targeted paclitaxel (PTX) delivery. <b>Methods</b>: Molecular docking simulations employed the MMP-2 crystal structure (PDB ID: 7XJO) to assess GPLGVRG peptide binding affinity. A cleavable, enzyme-sensitive peptide-PEG conjugate (Chol-PEG<sub>2K</sub>-GPLGVRG-PEG<sub>5K</sub>) was synthesized via small-molecule liquid-phase synthesis and characterized by <sup>1</sup>H NMR and MALDI-TOF MS. Liposomes incorporating this conjugate (S-Peps-PEG<sub>5K</sub>) were formulated to evaluate whether MMP-2-mediated peptide degradation triggers detachment of long-chain PEG moieties, thereby enhancing internalization by 4T1 breast cancer cells. Additionally, the effects of tumor microenvironmental pH (~6.5) and MMP-2 concentration on drug release dynamics were investigated. <b>Results</b>: Molecular docking revealed robust GPLGVRG-MMP-2 interactions, yielding a binding energy of −7.1 kcal/mol. The peptide formed hydrogen bonds with MMP-2 residues Tyr A:23 and Arg A:53 (bond lengths: 2.4–2.5 Å) and engaged in hydrophobic contacts, confirming MMP-2 as the primary recognition site. Formulations containing 5 mol% Chol-PEG<sub>2K</sub>-GPLGVRG-PEG<sub>5K</sub> combined with 0.15 µg/mL MMP-2 (S-Peps-PEG<sub>5K</sub> +MMP) exhibited superior internalization efficiency and significantly reduced clonogenic survival compared to controls. Notably, acidic pH (~6.5) induced MMP-2-mediated cleavage of the GPLGVRG peptide, accelerating S-Peps-PEG<sub>5K</sub> dissociation and facilitating drug release. <b>Conclusions</b>: MMP-2-responsive, cleavable PEGylated liposomes markedly improve PTX accumulation and controlled release at tumor sites by dynamically modulating their stealth properties, offering a promising strategy to enhance chemotherapy efficacy in breast cancer.https://www.mdpi.com/1424-8247/18/7/1042matrix metalloproteinasespaclitaxelcleavable PEGbreast cancer cellsmolecular dockingGPLGVRG peptide
spellingShingle Xingyu Zhao
Yinghuan Li
Matrix Metalloproteinase-2-Responsive Peptide-Modified Cleavable PEGylated Liposomes for Paclitaxel Delivery
Pharmaceuticals
matrix metalloproteinases
paclitaxel
cleavable PEG
breast cancer cells
molecular docking
GPLGVRG peptide
title Matrix Metalloproteinase-2-Responsive Peptide-Modified Cleavable PEGylated Liposomes for Paclitaxel Delivery
title_full Matrix Metalloproteinase-2-Responsive Peptide-Modified Cleavable PEGylated Liposomes for Paclitaxel Delivery
title_fullStr Matrix Metalloproteinase-2-Responsive Peptide-Modified Cleavable PEGylated Liposomes for Paclitaxel Delivery
title_full_unstemmed Matrix Metalloproteinase-2-Responsive Peptide-Modified Cleavable PEGylated Liposomes for Paclitaxel Delivery
title_short Matrix Metalloproteinase-2-Responsive Peptide-Modified Cleavable PEGylated Liposomes for Paclitaxel Delivery
title_sort matrix metalloproteinase 2 responsive peptide modified cleavable pegylated liposomes for paclitaxel delivery
topic matrix metalloproteinases
paclitaxel
cleavable PEG
breast cancer cells
molecular docking
GPLGVRG peptide
url https://www.mdpi.com/1424-8247/18/7/1042
work_keys_str_mv AT xingyuzhao matrixmetalloproteinase2responsivepeptidemodifiedcleavablepegylatedliposomesforpaclitaxeldelivery
AT yinghuanli matrixmetalloproteinase2responsivepeptidemodifiedcleavablepegylatedliposomesforpaclitaxeldelivery