4.7 Article

Comparison between the LCST and UCST Transitions of Double Thermoresponsive Diblock Copolymers: Insights into the Behavior of POEGMA in Alcohols

期刊

MACROMOLECULES
卷 45, 期 7, 页码 3221-3230

出版社

AMER CHEMICAL SOC
DOI: 10.1021/ma300374y

关键词

-

向作者/读者索取更多资源

Doubly thermoresponsive polymers consisting of a poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA) block displaying UCST behavior in alcohols and a block of poly(N-isopropylacrylamide) (PNIPAM) or poly-(N,N-diethylacrylamide) (PDEAM), each of which has an LCST in water, were synthesized using RAFT polymerization followed by simultaneous activated ester/amine and nucleophilic thiol-ene postpolymerization conversions. Upon heating aqueous solutions of POEGMA-b-PNIPAM, H-1 NMR spectroscopy confirmed a sudden decrease of the PNIPAM signals at the LCST, indicating dehydration and chain collapse. Dynamic light scattering (DLS) and turbidity measurements observed the macroscopic phase separation of the PNIPAM block at the same temperature. In 2-propanol, H-1 NMR spectroscopy showed a gradual decrease of the POEGMA signals over a range of more than 30 degrees C during its UCST transition, indicating early stages of chain crumpling up to 20 degrees C above the macroscopic phase separation. The OEG side chains were found to collapse onto the backbone starting at the ester linkages, indicating the most unfavorable enthalpic polymer-solvent interactions occur adjacent to the ester group. Although the diblock copolymers displayed a strong concentration-dependent cloud point, H-1 NMR spectroscopy revealed a concentration-independent desolvation, indicating the potential for applications that are not based on phase separation but on changes of polymer conformation. The phase separation occurred within a narrow temperature range of similar to 6 degrees C as evidenced by turbidity and DLS. This transition could be exploited to self-assemble POEGMA-b-PDEAM into micellar structures with POEGMA cores in 1-octanol. Cooling to similar to 15 degrees C below the cloud point was necessary to produce compact structures. Upon heating, the aggregates remained compact until redissolving entirely within a range of 1 degrees C, making the UCST of POEGMA in alcohols a valuable tool for reversible self-assembly applications.

作者

我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。

评论

主要评分

4.7
评分不足

次要评分

新颖性
-
重要性
-
科学严谨性
-
评价这篇论文

推荐

Article Engineering, Biomedical

Interactions of core cross-linked poly(2-oxazoline) and poly(2-oxazine) micelles with immune cells in human blood

Meike N. Leiske, May Lai, Thakshila Amarasena, Thomas P. Davis, Kristofer J. Thurecht, Stephen J. Kent, Kristian Kempe

Summary: The study demonstrates that PMeOx polymer structures show weaker interactions with immune cells in human blood, indicating their potential advantages in biomedical applications.

BIOMATERIALS (2021)

Article Chemistry, Multidisciplinary

Spatio-temporal analysis of nanoparticles in live tumor spheroids impacted by cell origin and density

Aria Ahmed-Cox, Elvis Pandzic, Stuart T. Johnston, Celine Heu, John McGhee, Friederike M. Mansfeld, Edmund J. Crampin, Thomas P. Davis, Renee M. Whan, Maria Kavallaris

Summary: Nanoparticles show promise in cancer therapy, but face challenges in clinical trials. Developing advanced 3D cell models like tumor spheroids can help evaluate nanoparticle designs and understand how different cell characteristics influence uptake. A new analysis platform, DONUTS, allows for spatial and temporal quantification of nanoparticle uptake in 3D tumor spheroids, offering insight into penetration kinetics and cell type variations.

JOURNAL OF CONTROLLED RELEASE (2022)

Article Biotechnology & Applied Microbiology

miR-99b-5p, miR-380-3p, and miR-485-3p are novel chemosensitizing miRNAs in high-risk neuroblastoma

Holly Holliday, Jessica Yang, Eoin Dodson, Iva Nikolic, Alvin Kamili, Madeleine Wheatley, Niantao Deng, Sarah Alexandrou, Thomas P. Davis, Maria Kavallaris, C. Elizabeth Caldon, Joshua McCarroll, Katleen De Preter, Pieter Mestdagh, Glenn M. Marshall, Kaylene J. Simpson, Jamie Fletcher, Alexander Swarbrick

Summary: This study discovered that miR-99b-5p, miR-380-3p, and miR-485-3p enhance the chemotherapeutic effects of doxorubicin in high-risk neuroblastoma. These miRNAs are often lost in patients and their low expression predicts poor survival outcomes.

MOLECULAR THERAPY (2022)

Article Multidisciplinary Sciences

Schwann cell endosome CGRP signals elicit periorbital mechanical allodynia in mice

Francesco De Logu, Romina Nassini, Alan Hegron, Lorenzo Landini, Dane D. Jensen, Rocco Latorre, Julia Ding, Matilde Marini, Daniel Souza Monteiro de Araujo, Paulina Ramirez-Garcia, Michael Whittaker, Jeffri Retamal, Mustafa Titiz, Alessandro Innocenti, Thomas P. Davis, Nicholas Veldhuis, Brian L. Schmidt, Nigel W. Bunnett, Pierangelo Geppetti

Summary: This study reveals that the CGRP-mediated neuronal/Schwann cell pathway mediates allodynia associated with neurogenic inflammation, contributing to the algesic action of CGRP in mice.

NATURE COMMUNICATIONS (2022)

Article Nanoscience & Nanotechnology

Engineering Polymers via Understanding the Effect of Anchoring Groups for Highly Stable Liquid Metal Nanoparticles

Xumin Huang, Tianhong Xu, Ao Shen, Thomas P. Davis, Ruirui Qiao, Shi-Yang Tang

Summary: This study investigates the effect of different anchoring groups on the stability of liquid metal nanoparticles (LMNPs), and finds that increasing the number of anchoring groups enhances the colloidal stability of LMNPs, while polymers bearing multidentate phosphonic acids provide the optimum chemical stability for LMNPs.

ACS APPLIED NANO MATERIALS (2022)

Article Biochemistry & Molecular Biology

Zwitterionic Amino Acid-Derived Polyacrylates as Smart Materials Exhibiting Cellular Specificity and Therapeutic Activity

Meike N. Leiske, Zihnil A. I. Mazrad, Aykut Zelcak, Kanu Wahi, Thomas P. Davis, Joshua A. McCarroll, Jeff Holst, Kristian Kempe

Summary: This study presents a method for synthesizing new amino acid-containing, cell-specific, therapeutically active polymers. Starting materials were amino acids, which were used to prepare tailored polymers with different amino acids in the side chain. The reversible addition-fragmentation chain-transfer (RAFT) polymerization of acrylate monomers resulted in polymers with narrow size distribution. Glutamate-functionalized, zwitterionic polymers exhibited high cytocompatibility and cellular specificity, showing association with cancer cell lines but not with nontumor fibroblasts. Cellular uptake experiments and confocal laser scanning microscopy confirmed energy-dependent uptake mechanisms and localization of the polymers in cellular lysosomes. Copolymers with a specific monomer ratio of Glu acrylate and BzlSer acrylate demonstrated targeted cytotoxicity against cancer cells while leaving fibroblasts unaffected. These results highlight the importance of incorporating biologically derived materials in synthetic polymers and the potential of zwitterionic, amino acid-derived materials for cellular targeting.

BIOMACROMOLECULES (2022)

Article Engineering, Biomedical

Aerosol delivery of star polymer-siRNA nanoparticles as a therapeutic strategy to inhibit lung tumor growth

Z. Ma, S. W. Wong, H. Forgham, L. Esser, M. Lai, M. N. Leiske, K. Kempe, G. Sharbeen, J. Youkhana, F. Mansfeld, J. F. Quinn, P. A. Phillips, T. P. Davis, M. Kavallaris, J. A. McCarroll

Summary: The study demonstrated that star-shaped siRNA nanoparticles can effectively inhibit target gene expression in lung cancer cells and delay tumor growth in mouse lung tumors. This provides a proof-of-concept for aerosol delivery of star-siRNA nanoparticles as a novel therapeutic strategy to inhibit lung tumor growth.

BIOMATERIALS (2022)

Article Engineering, Biomedical

Sustained endosomal release of a neurokinin-1 receptor antagonist from nanostars provides long-lasting relief of chronic pain

Rocco Latorre, Paulina D. Ramirez-Garcia, Alan Hegron, James L. Grace, Jeffri S. Retamal, Priyank Shenoy, Mai Tran, Luigi Aurelio, Bernard Flynn, Daniel P. Poole, Rafael Klein-Cloud, Dane D. Jensen, Thomas P. Davis, Brian L. Schmidt, John F. Quinn, Michael R. Whittaker, Nicholas A. Veldhuis, Nigel W. Bunnett

Summary: Stable star polymer nanostars that release antagonists continuously for 24 hours provide effective and long-lasting relief from chronic pain by disrupting endosomal signaling.

BIOMATERIALS (2022)

Article Chemistry, Physical

Thiol-responsive lyotropic liquid crystals exhibit triggered phase re-arrangement and hydrogen sulfide (H2S) release

Matthew C. Urquhart, Francesca Ercole, Andrew J. Clulow, Thomas P. Davis, Michael R. Whittaker, Ben J. Boyd, John F. Quinn

Summary: This study discovers that an amphiphilic trisulfide can alter the behavior of lipid particles and enable triggered release of H2S, providing potential applications in stimuli-responsive drug delivery systems.

JOURNAL OF COLLOID AND INTERFACE SCIENCE (2022)

Article Polymer Science

Well-Defined Tetrazole-Functional Copolymers as Macromolecular Ligands for Luminescent Ir(III) and Re(I) Metal Species: Synthesis, Photophysical Properties and Application in Bioimaging

Elena Dallerba, David Hartnell, Mark J. Hackett, Massimiliano Massi, Andrew B. Lowe

Summary: Copolymers containing luminescent iridium and iridium/rhenium fragments were prepared through modification of a precursor polymer. These materials exhibit excellent luminescent properties and have potential applications in tissue imaging.

MACROMOLECULAR CHEMISTRY AND PHYSICS (2022)

Article Polymer Science

Tetrazole as a Carboxylic Acid Isostere and the Synthesis of All Amine-Based Polyampholytes

Amber Nguyen, Elena Dallerba, Andrew B. Lowe

Summary: A new family of polyampholytes (PAMs) with nitrogen functional groups as both the basic and acidic groups is described. The synthesis of the well-defined statistical PAMs is confirmed through various spectroscopic techniques. Aqueous electrophoresis results indicate the isoelectric points (pI) of the PAMs, which are somewhat insensitive to the copolymer composition.

MACROMOLECULAR RAPID COMMUNICATIONS (2022)

Article Polymer Science

Heat-Induced Living Crystallization-Driven Self-Assembly: The Effect of Temperature and Polymer Composition on the Assembly and Disassembly of Poly(2-oxazoline) Nanorods

John R. Finnegan, Thomas P. Davis, Kristian Kempe

Summary: Poly(2-oxazoline)s (POx) are promising biomaterials with biocompatibility and versatile functionality. This study successfully prepared POx nanorods of tunable length using a heat-induced living crystallization-driven self-assembly (CDSA) method and examined the essential steps of this process. The disassembly and freeze-drying protocols of the POx nanorods were also investigated.

MACROMOLECULES (2022)

Article Materials Science, Biomaterials

Targeting endosomal receptors, a new direction for polymers in nanomedicine

Paulina D. Ramirez-Garcia, Nicholas A. Veldhuis, Nigel W. Bunnett, Thomas P. Davis

Summary: In this article, we propose a new opportunity to target intracellular compartments by delivering antagonists via nanoparticles to G-protein coupled receptors. We specifically discuss the application of this approach in antagonizing endosomal receptors involved in pain for developing long-lasting analgesics, and also highlight the potential broader applications. We also discuss the materials used and provide design requirements for future successful applications.

JOURNAL OF MATERIALS CHEMISTRY B (2023)

Review Chemistry, Multidisciplinary

Exploring Peptido-Nanocomposites in the Context of Amyloid Diseases

Nicholas Andrikopoulos, Huayuan Tang, Yue Wang, Xiufang Liang, Yuhuan Li, Thomas P. Davis, Pu Chun Ke

Summary: Therapeutic peptides are important drugs that specifically target abnormal protein-protein interactions associated with amyloid diseases. The use of nanoparticles in combination with peptide drugs has emerged as a promising strategy for enhancing their efficacy against amyloid aggregation and cellular inflammation. However, there is still a lack of understanding of the chemistry and function of peptido-nanocomposites, and a systematic analysis of their application against a range of amyloid pathogeneses is missing.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2023)

Article Polymer Science

Protected amine-functional initiators for the synthesis of α-amine homo- and heterotelechelic poly(2-ethyl-2-oxazoline)s

Zihnil A. I. Mazrad, May Lai, Thomas P. Davis, Joseph A. Nicolazzo, Kristofer J. Thurecht, Meike N. Leiske, Kristian Kempe

Summary: This study explores the application of a new initiator in polymer synthesis. The results show that this initiator can achieve a higher degree of control over the polymerization process under irradiation, resulting in well-defined polymers. In addition, tailored amine-based polymers can be prepared by using different terminating agents.

POLYMER CHEMISTRY (2022)

暂无数据