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New Progress in Polymer Self-Assembly

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Smart and Functional Polymers".

Deadline for manuscript submissions: closed (5 September 2024) | Viewed by 17806

Special Issue Editor


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Guest Editor
School of Medicine and Health, Harbin Institute of Technology, Harbin 150080, China
Interests: molecular self-assembly; amphiphiles; dissipative self-assembly; porous materials

Special Issue Information

Dear Colleagues,

Polymer self-assembly is one of the bridges connecting chemical science and biological science, as a large number of vital movements are dependent on the self-assembly of biomacromolecules such as polysaccharides, proteins, and nucleic acids. Moreover, polymer self-assembly is also a powerful tool that can be used to create functional materials. Therefore, polymer self-assembly has attracted extensive interest in the research community, including from chemists, biologists, and material scientists.

This Special Issue aims to present the recent advances in the research on polymer self-assembly, including on new concepts, theories, methods, structures, and functions. Studies and reviews presenting original research on polymer self-assembly are of interest. Topics of interest include but are not limited to the following:

  • Basic principles of polymer self-assembly;
  • Newly self-assembled structures;
  • Self-assembly of biomacromolecules;
  • Supramolecular polymers;
  • Polymer self-assembly outside of thermodynamic equilibrium;
  • Functional structures and materials fabricated by polymer self-assembly.

Dr. Guangtong Wang
Guest Editor

Manuscript Submission Information

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Keywords

  • polymer self-assembly
  • supramolecular polymers
  • functional materials

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Published Papers (9 papers)

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Research

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12 pages, 2881 KiB  
Article
Self-Assembly of the Block Copolymer Containing Discotic Mesogens Driven by Liquid Crystalline Ordering Effect
by Xiaojian Hou, Lingjuan Hu, Huanzhi Yang, Bixin Jin, Yunjun Luo and Xiaoyu Li
Polymers 2024, 16(23), 3339; https://doi.org/10.3390/polym16233339 - 28 Nov 2024
Viewed by 371
Abstract
Block copolymers (BCPs) have attracted considerable attention due to their ability to form a variety of complex assemblies with diverse morphologies and functions in solution. By incorporating liquid crystalline (LC) moieties, the LC side chains significantly affect the morphologies and sizes of BCP [...] Read more.
Block copolymers (BCPs) have attracted considerable attention due to their ability to form a variety of complex assemblies with diverse morphologies and functions in solution. By incorporating liquid crystalline (LC) moieties, the LC side chains significantly affect the morphologies and sizes of BCP assemblies. In this study, we synthesized the copolymer with an LC block containing triphenylene (HAT) discotic mesogen and short methylene side chains. By enhancing the π–π interaction between triphenylene discotic mesogens, and doping the discotic mesogens, the LC orderedness was significantly enhanced and able to dictate the self-assembly behaviors of the BCP in solution. Additionally, the lengths of resultant fibrillar micelles were easily tuned by adjusting the dopant content. More interestingly, two growth modes, nucleation growth and coupling, were observed during the formation of fibrils. Consequently, with long-term aging and sufficient concentration, a large portion of these fibrils underwent end-to-end coupling to form long fibrils, allowing the formation of organogel via inter-fibrillar entanglement. Full article
(This article belongs to the Special Issue New Progress in Polymer Self-Assembly)
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13 pages, 2664 KiB  
Article
Bio-Based Epoxy Vitrimers with Excellent Properties of Self-Healing, Recyclability, and Welding
by Jianrong Xia, Shuyun Li, Renjin Gao, Yuchi Zhang, Liwei Wang, Yuansong Ye, Changlin Cao and Hanyu Xue
Polymers 2024, 16(15), 2113; https://doi.org/10.3390/polym16152113 - 24 Jul 2024
Cited by 2 | Viewed by 1333
Abstract
The development of more recyclable materials is a key requirement for a transition towards a more circular economy. Thanks to exchange reactions, vitrimer, an attractive alternative for recyclable materials, is an innovative class of polymers that is able to change its topology without [...] Read more.
The development of more recyclable materials is a key requirement for a transition towards a more circular economy. Thanks to exchange reactions, vitrimer, an attractive alternative for recyclable materials, is an innovative class of polymers that is able to change its topology without decreasing its connectivity. In this work, a bisphenol compound (VP) was prepared from saturated cardanol, i.e., 3−pentadecylphenol and vanillyl alcohol. Then, VP was epoxidized to obtain epoxide (VPGE). Finally, VPGE and citric acid (CA) were polymerized in the presence of catalyst TBD to prepare a fully bio−based vitrimer based on transesterification. The results from differential scanning calorimetry (DSC) showed that the VPGE/CA system could be crosslinked at around 163 °C. The cardanol−derived vitrimers had good network rearrangement properties. Meanwhile, because of the dynamic structural elements in the network, the material was endowed with excellent self−healing, welding, and recyclability. Full article
(This article belongs to the Special Issue New Progress in Polymer Self-Assembly)
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11 pages, 1813 KiB  
Article
Enhanced Thermal and Mechanical Properties of Cardanol Epoxy/Clay-Based Nanocomposite through Girard’s Reagent
by Ji Xu, Lingxiao Jia, Qixin Lan and Daheng Wu
Polymers 2024, 16(11), 1528; https://doi.org/10.3390/polym16111528 - 29 May 2024
Viewed by 861
Abstract
The green and environmentally friendly cardanol epoxy resin has a bright application prospect, but its insufficient thermal/mechanical properties seriously hinder its application. Adding nanoclay to polymer matrix is an effective method to enhance the thermal/mechanical properties of material, but the dispersion and compatibility [...] Read more.
The green and environmentally friendly cardanol epoxy resin has a bright application prospect, but its insufficient thermal/mechanical properties seriously hinder its application. Adding nanoclay to polymer matrix is an effective method to enhance the thermal/mechanical properties of material, but the dispersion and compatibility of nanoclay in epoxy resin remain to be solved. In this work, active Girard’s reagent clay (PG-clay) and non-active Girard’s reagent clay (NG-clay) were prepared by using acethydrazide trimethylammonium chloride (Girard’s reagent) as the modifier, and cardanol epoxy resin/G-clay nanocomposites were synthesized by the “clay slurry composite method”. The results showed that both PG-clay and NG-clay were dispersed in the epoxy matrix in the form of random exfoliation/intercalation, which effectively improved the thermal/mechanical properties of the composites. Tg of the cardanol epoxy resin has raised from 19.8 °C to 38.1 °C (4 wt.% PG-clay). When the mass fraction of clay is 4%, the tensile strength of the non-reactive NG-clay increases by 128%, and the elongation at break also increases by 101%. Simultaneously, the active PG-clay can participate in the curing reaction of epoxy resin due to the amino group, forming a chemical bond between the clay layer and the resin matrix and establishing a strong interfacial force. The tensile strength of the composite is increased by 970%, and the elongation at break is also increased by 428%. This research demonstrates that the cardanol epoxy resin/G-clay nanocomposite stands as a highly promising candidate for bio-based epoxy resin materials. Full article
(This article belongs to the Special Issue New Progress in Polymer Self-Assembly)
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16 pages, 16857 KiB  
Article
Cationic Azobenzenes as Light-Responsive Crosslinkers for Alginate-Based Supramolecular Hydrogels
by Miriam Di Martino, Lucia Sessa, Barbara Panunzi, Rosita Diana, Stefano Piotto and Simona Concilio
Polymers 2024, 16(9), 1233; https://doi.org/10.3390/polym16091233 - 28 Apr 2024
Viewed by 1540
Abstract
Azobenzene photoswitches are fundamental components in contemporary approaches aimed at light-driven control of intelligent materials. Significant endeavors are directed towards enhancing the light-triggered reactivity of azobenzenes for such applications and obtaining water-soluble molecules able to act as crosslinkers in a hydrogel. Here, we [...] Read more.
Azobenzene photoswitches are fundamental components in contemporary approaches aimed at light-driven control of intelligent materials. Significant endeavors are directed towards enhancing the light-triggered reactivity of azobenzenes for such applications and obtaining water-soluble molecules able to act as crosslinkers in a hydrogel. Here, we report the rational design and the synthesis of azobenzene/alginate photoresponsive hydrogels endowed with fast reversible sol–gel transition. We started with the synthesis of three cationic azobenzenes (AZOs A, B, and C) and then incorporated them in sodium alginate (SA) to obtain photoresponsive supramolecular hydrogels (SMHGs). The photoresponsive properties of the azobenzenes were investigated by UV–Vis and 1H NMR spectroscopy. Upon irradiation with 365 nm UV light, the azobenzenes demonstrated efficient trans-to-cis isomerization, with complete isomerization occurring within seconds. The return to the trans form took several hours, with AZO C exhibiting the fastest return, possibly due to higher trans isomer stability. In the photoresponsive SMHGs, the minimum gelation concentration (MGC) of azobenzenes was determined for different compositions, indicating that small amounts of azobenzenes could induce gel formation, particularly in 5 wt% SA. Upon exposure to 365 nm UV light, the SMHGs exhibited reversible gel–sol transitions, underscoring their photoresponsive nature. This research offers valuable insights into the synthesis and photoresponsive properties of cationic, water-soluble azobenzenes, as well as their potential application in the development of photoresponsive hydrogels. Full article
(This article belongs to the Special Issue New Progress in Polymer Self-Assembly)
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26 pages, 3871 KiB  
Article
On the Fractionation and Physicochemical Characterisation of Self-Assembled Chitosan–DNA Polyelectrolyte Complexes
by Ayesha Sajid, Matteo Castronovo and Francisco M. Goycoolea
Polymers 2023, 15(9), 2115; https://doi.org/10.3390/polym15092115 - 28 Apr 2023
Cited by 3 | Viewed by 1680
Abstract
Chitosan is extensively studied as a carrier for gene delivery and is an attractive non-viral gene vector owing to its polycationic, biodegradable, and biocompatible nature. Thus, it is essential to understand the chemistry of self-assembled chitosan–DNA complexation and their structural and functional properties, [...] Read more.
Chitosan is extensively studied as a carrier for gene delivery and is an attractive non-viral gene vector owing to its polycationic, biodegradable, and biocompatible nature. Thus, it is essential to understand the chemistry of self-assembled chitosan–DNA complexation and their structural and functional properties, enabling the formation of an effective non-viral gene delivery system. In this study, two parent chitosans (samples NAS-032 and NAS-075; Mw range ~118–164 kDa) and their depolymerised derivatives (deploy nas-032 and deploy nas-075; Mw range 6–14 kDa) with degrees of acetylation 43.4 and 4.7%, respectively, were used to form polyelectrolyte complexes (PECs) with DNA at varying [–NH3+]/[–PO4] (N/P) molar charge ratios. We investigated the formation of the PECs using ζ-potential, asymmetric flow field-flow fractionation (AF4) coupled with multiangle light scattering (MALS), refractive index (RI), ultraviolet (UV) and dynamic light scattering (DLS) detectors, and TEM imaging. PEC formation was confirmed by ζ-potential measurements that shifted from negative to positive values at N/P ratio ~2. The radius of gyration (Rg) was determined for the eluting fractions by AF4-MALS-RI-UV, while the corresponding hydrodynamic radius (Rh), by the DLS data. We studied the influence of different cross-flow rates on AF4 elution patterns for PECs obtained at N/P ratios 5, 10, and 20. The determined rho shape factor (ρ = Rg/Rh) values for the various PECs corresponded with a sphere morphology (ρ ~0.77–0.85), which was consistent with TEM images. The results of this study represent a further step towards the characterisation of chitosan–DNA PECs by the use of multi-detection AF4 as an important tool to fractionate and infer aspects of their morphology. Full article
(This article belongs to the Special Issue New Progress in Polymer Self-Assembly)
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13 pages, 21954 KiB  
Article
The Dual Modification of PNIPAM and β-Cyclodextrin Grafted on Hyaluronic Acid as Self-Assembled Nanogel for Curcumin Delivery
by Tisana Kaewruethai, Yuan Lin, Qian Wang and Jittima Amie Luckanagul
Polymers 2023, 15(1), 116; https://doi.org/10.3390/polym15010116 - 27 Dec 2022
Cited by 9 | Viewed by 3033
Abstract
Curcumin is an extract of turmeric (Curcuma longa) which possesses anti-inflammatory, anti-cancer and wound-healing effects and has been used as an active compound in biomedical research for many years. However, its poor solubility presents challenges for its use in drug delivery [...] Read more.
Curcumin is an extract of turmeric (Curcuma longa) which possesses anti-inflammatory, anti-cancer and wound-healing effects and has been used as an active compound in biomedical research for many years. However, its poor solubility presents challenges for its use in drug delivery systems. A modified nanogel delivery system, with PNIPAM and β-cyclodextrin grafted onto hyaluronic acid (PNCDHA), was utilized to enhance the solubility. The polymer was characterized by NMR, and the inclusion complex between curcumin and β-cyclodextrin was confirmed by FTIR. The potential of this PNCDHA polymer complex as a drug delivery vehicle was supported by a curcumin encapsulation efficiency of 93.14 ± 5.6% and the release of encapsulated curcumin at 37 °C. At a concentration of 0.5% w/v in water, PNCDHA nanogels were biocompatible with fibroblast cell line (L929) up to a curcumin concentration of 50 µM. There was a direct concentration between curcumin loading and cellular internalization. A more detailed study of the cellular internalization of PNCDHA nanogel should be considered in order to clarify cellular delivery mechanisms and to assess how its viability as a carrier may be optimized. Full article
(This article belongs to the Special Issue New Progress in Polymer Self-Assembly)
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Review

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30 pages, 6431 KiB  
Review
Self-Assembly of Polymers and Their Applications in the Fields of Biomedicine and Materials
by Lina Hu, Shujing Zhou, Xiumei Zhang, Chengyang Shi, Yifan Zhang and Xiaoyi Chen
Polymers 2024, 16(15), 2097; https://doi.org/10.3390/polym16152097 - 23 Jul 2024
Cited by 3 | Viewed by 2544
Abstract
Polymer self-assembly can prepare various shapes and sizes of pores, making it widely used. The complexity and diversity of biomolecules make them a unique class of building blocks for precise assembly. They are particularly suitable for the new generation of biomaterials integrated with [...] Read more.
Polymer self-assembly can prepare various shapes and sizes of pores, making it widely used. The complexity and diversity of biomolecules make them a unique class of building blocks for precise assembly. They are particularly suitable for the new generation of biomaterials integrated with life systems as they possess inherent characteristics such as accurate identification, self-organization, and adaptability. Therefore, many excellent methods developed have led to various practical results. At the same time, the development of advanced science and technology has also expanded the application scope of self-assembly of synthetic polymers. By utilizing this technology, materials with unique shapes and properties can be prepared and applied in the field of tissue engineering. Nanomaterials with transparent and conductive properties can be prepared and applied in fields such as electronic displays and smart glass. Multi-dimensional, controllable, and multi-level self-assembly between nanostructures has been achieved through quantitative control of polymer dosage and combination, chemical modification, and composite methods. Here, we list the classic applications of natural- and artificially synthesized polymer self-assembly in the fields of biomedicine and materials, introduce the cutting-edge technologies involved in these applications, and discuss in-depth the advantages, disadvantages, and future development directions of each type of polymer self-assembly. Full article
(This article belongs to the Special Issue New Progress in Polymer Self-Assembly)
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14 pages, 2316 KiB  
Review
Polymer-Based Self-Assembled Drug Delivery Systems for Glaucoma Treatment: Design Strategies and Recent Advances
by Hao Sun, Guangtong Wang, Qingying Feng and Shaoqin Liu
Polymers 2023, 15(22), 4466; https://doi.org/10.3390/polym15224466 - 20 Nov 2023
Cited by 4 | Viewed by 2474
Abstract
Glaucoma has become the world’s leading cause of irreversible blindness, and one of its main characteristics is high intraocular pressure. Currently, the non-surgical drug treatment scheme to reduce intraocular pressure is a priority method for glaucoma treatment. However, the complex and special structure [...] Read more.
Glaucoma has become the world’s leading cause of irreversible blindness, and one of its main characteristics is high intraocular pressure. Currently, the non-surgical drug treatment scheme to reduce intraocular pressure is a priority method for glaucoma treatment. However, the complex and special structure of the eye poses significant challenges to the treatment effect and safety adherence of this drug treatment approach. To address these challenges, the application of polymer-based self-assembled drug delivery systems in glaucoma treatment has emerged. This review focuses on the utilization of polymer-based self-assembled structures or materials as important functional and intelligent carriers for drug delivery in glaucoma treatment. Various drug delivery systems, such as eye drops, hydrogels, and contact lenses, are discussed. Additionally, the review primarily summarizes the design strategies and methods used to enhance the treatment effect and safety compliance of these polymer-based drug delivery systems. Finally, the discussion delves into the new challenges and prospects of employing polymer-based self-assembled drug delivery systems for the treatment of glaucoma. Full article
(This article belongs to the Special Issue New Progress in Polymer Self-Assembly)
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45 pages, 16372 KiB  
Review
Supramolecular Combination Cancer Therapy Based on Macrocyclic Supramolecular Materials
by Yilin Li, Yuteng Su, Zhaoxiang Li and Yueyue Chen
Polymers 2022, 14(22), 4855; https://doi.org/10.3390/polym14224855 - 11 Nov 2022
Cited by 8 | Viewed by 2840
Abstract
Supramolecular combination therapy adopts supramolecular materials to design intelligent drug delivery systems with different strategies for cancer treatments. Thereinto, macrocyclic supramolecular materials play a crucial role in encapsulating anticancer drugs to improve anticancer efficiency and decrease toxicity towards normal tissue by host–guest interaction. [...] Read more.
Supramolecular combination therapy adopts supramolecular materials to design intelligent drug delivery systems with different strategies for cancer treatments. Thereinto, macrocyclic supramolecular materials play a crucial role in encapsulating anticancer drugs to improve anticancer efficiency and decrease toxicity towards normal tissue by host–guest interaction. In general, chemotherapy is still common therapy for solid tumors in clinics. However, supramolecular combination therapy can overcome the limitations of the traditional single-drug chemotherapy in the laboratory findings. In this review, we summarized the combination chemotherapy, photothermal chemotherapy, and gene chemotherapy based on macrocyclic supramolecular materials. Finally, the application prospects in supramolecular combination therapy are discussed. Full article
(This article belongs to the Special Issue New Progress in Polymer Self-Assembly)
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