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Articles de revues sur le sujet « Self-Assembly of block copolymers »

Auteur : Grafiati

Publié le 7 juillet 2024

Mis à jour le 19 juillet 2025

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1

Abetz, Volker. "Self-Assembly of Block Copolymers." Polymers 12, no. 4 (2020): 794. http://dx.doi.org/10.3390/polym12040794.

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Kuperkar, Ketan, Dhruvi Patel, Leonard Ionut Atanase, and Pratap Bahadur. "Amphiphilic Block Copolymers: Their Structures, and Self-Assembly to Polymeric Micelles and Polymersomes as Drug Delivery Vehicles." Polymers 14, no. 21 (2022): 4702. http://dx.doi.org/10.3390/polym14214702.

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Self-assembly of amphiphilic block copolymers display a multiplicity of nanoscale periodic patterns proposed as a dominant tool for the ‘bottom-up’ fabrication of nanomaterials with different levels of ordering. The present review article focuses on the recent updates to the self-association of amphiphilic block copolymers in aqueous media into varied core-shell morphologies. We briefly describe the block copolymers, their types, microdomain formation in bulk and micellization in selective solvents. We also discuss the characteristic features of block copolymers nanoaggregates viz., polymer micelles (PMs) and polymersomes. Amphiphilic block copolymers (with a variety of hydrophobic blocks and hydrophilic blocks; often polyethylene oxide) self-assemble in water to micelles/niosomes similar to conventional nonionic surfactants with high drug loading capacity. Double hydrophilic block copolymers (DHBCs) made of neutral block-neutral block or neutral block-charged block can transform one block to become hydrophobic under the influence of a stimulus (physical/chemical/biological), and thus induced amphiphilicity and display self-assembly are discussed. Different kinds of polymer micelles (viz. shell and core-cross-linked, core-shell-corona, schizophrenic, crew cut, Janus) are presented in detail. Updates on polymerization-induced self-assembly (PISA) and crystallization-driven self-assembly (CDSA) are also provided. Polyion complexes (PICs) and polyion complex micelles (PICMs) are discussed. Applications of these block copolymeric micelles and polymersomes as nanocarriers in drug delivery systems are described.

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Yoon, Jongseung, Wonmok Lee, and Edwin L. Thomas. "Self-Assembly of Block Copolymers for Photonic-Bandgap Materials." MRS Bulletin 30, no. 10 (2005): 721–26. http://dx.doi.org/10.1557/mrs2005.270.

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AbstractSelf-assembled block copolymer systems with an appropriate molecular weight to produce a length scale that will interact with visible light are an alternative platform material for the fabrication of large-area, well-ordered photonic-bandgap structures at visible and near-IR frequencies.Over the past years, one-, two-, and three-dimensional photonic crystals have been demonstrated with various microdomain structures created through microphase separation of block copolymers. The size and shape of periodic microstructures of block copolymers can be readily tuned by molecular weight, relative composition of the copolymer, and blending with homopolymers or plasticizers.The versatility of photonic crystals based on block copolymers is further increased by incorporating inorganic nanoparticles or liquid-crystalline guest molecules (or using a liquid-crystalline block), or by selective etching of one of the microdomains and backfilling with high-refractive-index materials. This article presents an overview of photonic-bandgap materials enabled by self-assembled block copolymers and discusses the morphology and photonic properties of block-copolymer-based photonic crystals containing nanocomposite additives.We also provide a view of the direction of future research, especially toward novel photonic devices.

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Ma, Shuhui, Yushuang Hou, Jinlin Hao, Cuncai Lin, Jiawei Zhao, and Xin Sui. "Well-Defined Nanostructures by Block Copolymers and Mass Transport Applications in Energy Conversion." Polymers 14, no. 21 (2022): 4568. http://dx.doi.org/10.3390/polym14214568.

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With the speedy progress in the research of nanomaterials, self-assembly technology has captured the high-profile interest of researchers because of its simplicity and ease of spontaneous formation of a stable ordered aggregation system. The self-assembly of block copolymers can be precisely regulated at the nanoscale to overcome the physical limits of conventional processing techniques. This bottom-up assembly strategy is simple, easy to control, and associated with high density and high order, which is of great significance for mass transportation through membrane materials. In this review, to investigate the regulation of block copolymer self-assembly structures, we systematically explored the factors that affect the self-assembly nanostructure. After discussing the formation of nanostructures of diverse block copolymers, this review highlights block copolymer-based mass transport membranes, which play the role of “energy enhancers” in concentration cells, fuel cells, and rechargeable batteries. We firmly believe that the introduction of block copolymers can facilitate the novel energy conversion to an entirely new plateau, and the research can inform a new generation of block copolymers for more promotion and improvement in new energy applications.

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Benmouna, A., R. Benmouna, M. R. Bockstaller, and I. F. Hakem. "Self-Organization Schemes towards Thermodynamic Stable Bulk Heterojunction Morphologies: A Perspective on Future Fabrication Strategies of Polymer Photovoltaic Architectures." Advances in Physical Chemistry 2013 (April 16, 2013): 1–8. http://dx.doi.org/10.1155/2013/948189.

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Research efforts to improve our understanding of electronic polymers are developing fast because of their promising advantages over silicon in photovoltaic solar cells. A major challenge in the development of polymer photovoltaic devices is the viable fabrication strategies of stable bulk heterojunction architecture that will retain functionality during the expected lifetime of the device. Block copolymer self-assembly strategies have attracted particular attention as a scalable means toward thermodynamically stable microstructures that combine the ideal geometrical characteristics of a bulk heterojunction with the fortuitous combination of properties of the constituent blocks. Two primary routes that have been proposed in the literature involve the coassembly of block copolymers in which one domain is a hole conductor with the electron-conducting filler (such as fullerene derivatives) or the self-assembly of block copolymers in which the respective blocks function as hole and electron conductor. Either way has proven difficult because of the combination of synthetic challenges as well as the missing understanding of the complex governing parameters that control structure formation in semiconducting block copolymer blends. This paper summarizes important findings relating to structure formation of block copolymer and block copolymer/nanoparticle blend assembly that should provide a foundation for the future design of block copolymer-based photovoltaic systems.

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Xie, Yihui, Nicolas Moreno, Victor M. Calo, et al. "Synthesis of highly porous poly(tert-butyl acrylate)-b-polysulfone-b-poly(tert-butyl acrylate) asymmetric membranes." Polymer Chemistry 7, no. 18 (2016): 3076–89. http://dx.doi.org/10.1039/c6py00215c.

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For the first time, self-assembly and non-solvent induced phase separation was applied to polysulfone-based linear block copolymers, reaching mechanical stability much higher than other block copolymer membranes used in this method, which were mainly based on polystyrene blocks.

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Wang, Zihao, Susu Tao, Yanyan Chu, Xiaoyan Xu, and Qinggang Tan. "Diameter of Carbon Nanotube-Directed Self-Assembly of Amphiphilic Block Copolymers." Materials 12, no. 10 (2019): 1606. http://dx.doi.org/10.3390/ma12101606.

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The cooperative self-assembly of nanoparticles and amphiphilic block copolymers has attracted increasing interests as it offers effective routes to achieve nanocomposite supramolecular structures with desired structure and properties. The incorporation of nanoparticles usually tunes the self-assembly structure of block copolymers, as the copolymer–nanoparticle interactions may change the relative volume ratio of hydrophobic block/hydrophilic block copolymers. It should be noted that the micro-size length and the strong nonpolar feature of carbon nanotubes (CNTs) may cause the block copolymer–CNT interactions to differ from the the block copolymer–nanoparticle interactions. Herein, we show that the diameter of CNTs and the copolymer/CNT ratio have a profound effect on the self-assembly behavior of amphiphilic block copolymers. Upon the addition of carboxylated multi-walled carbon nanotubes (c-MWCNTs, diameter <8 nm,) to the methoxy polyethylene glycol-poly (D,L-lactic acid) (MPEG-PDLLA) solution, it is difficult to observe the c-MWCNTs directly in TEM images. However, it has been found that they form supramolecular nanocomposite structures with MPEG-PDLLA. Moreover, these supramolecular structures transform from core–shell spherical micelles into rod-like micelles and then into large composite aggregates with the increase of the c-MWCNT addition. However, in the case of the addition of c-MWCNTs with a diameter of 30–50 nm, the dispersed c-MWCNTs and spherical core–shell micelles could be observed simultaneously in the TEM images at a low c-MWCNT addition, and then the micelle structure disappeared and only well-dispersed c-MWNTs were observed in TEM images at a high c-MWCNT addition. A possible model was proposed to explain the rule of CNTs participating in the formation of copolymer/CNT nanocomposite structures. It was also shown that as-prepared copolymer/CNT supramolecular nanocomposites could be used as drug carriers, enabling the adjustment of the drug loading and release time.

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Choi, Young Joo, Hyeong Min Jin, Bong Hoon Kim, Ju Young Kim, and Sang Ouk Kim. "Self-Assembly Nanofabrication via Mussel-Inspired Interfacial Engineering." Applied Mechanics and Materials 229-231 (November 2012): 2749–52. http://dx.doi.org/10.4028/www.scientific.net/amm.229-231.2749.

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We present that polydopamineassistedinterfacial engineering can be synergistically integratedwith block copolymer lithography for surface nanopatterningof low-surface-energy substrate materials, includingTeflon, graphene, and gold. Block copolymer lithography is aself-assembly based nanofabrication that holds greatpromise for sub-10-nm scale patterning. The directed self-assemblyof block copolymers into device-oriented nanopatternsgenerally requires organic modification of a substrate surface.In this work, the versatility of the polydopamine treatment was demonstrated by the surface modification.

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Bailly, Nathalie, Gwenaelle Pound-Lana, and Bert Klumperman. "Synthesis, Characterization, and Self-Assembly of Poly(N-vinylpyrrolidone)-block-poly(vinyl acetate)." Australian Journal of Chemistry 65, no. 8 (2012): 1124. http://dx.doi.org/10.1071/ch12185.

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Poly(N-vinylpyrrolidone)-block-poly(vinyl acetate) (PVP-b-PVAc) block copolymers of varying molar mass and hydrophobic block lengths were synthesized by xanthate-mediated radical polymerization. In order to control the molar mass of the hydrophilic PVP block, a xanthate chain transfer agent, S-(2-cyano-2-propyl) O-ethyl xanthate, was used. The PVP-b-PVAc block copolymer is composed of a hydrophilic and hydrophobic segment, and has the ability to self-assemble in aqueous solution. The PVP-b-PVAc block copolymers were characterized by 1H NMR spectroscopy to confirm their self-assembly in water. The critical micelle concentration was determined by fluorescence spectroscopy. A combination of dynamic light scattering, transmission electron microscopy, and static light scattering was used to further characterize the self-assembly of the block copolymers in water.

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Tirrell, Matthew V., and Alexander Katz. "Self-Assembly in Materials Synthesis." MRS Bulletin 30, no. 10 (2005): 700–704. http://dx.doi.org/10.1557/mrs2005.205.

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AbstractThe synthesis of materials via self-assembly typically involves the spontaneous and reversible organization of small building blocks for the purpose of creating conglomerate structures over larger length scales. This introductory article describes self-assembly processes on several length scales, from subnanometer up to millimeter scales, and briefly summarizes some of the incredible diversity of materials that exhibit selfassembly. Articles in this issue cover self-assembly using zeolitic structures, organic molecular crystals, block copolymers, surfactants, mesoscale templates, and soluble crystallization additives. Keywords: block copolymers, materials synthesis, self-assembly, surfactants, templates, zeolites.

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Schmalz, Holger, and Volker Abetz. "Block Copolymers with Crystallizable Blocks: Synthesis, Self-Assembly and Applications." Polymers 14, no. 4 (2022): 696. http://dx.doi.org/10.3390/polym14040696.

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Block copolymers with crystallizable blocks are a highly interesting class of materials owing to their unique self-assembly behaviour both in bulk and solution. This Special Issue brings together new developments in the synthesis and self-assembly of semicrystalline block copolymers and also addresses potential applications of these exciting materials.

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Mai, Yiyong, and Adi Eisenberg. "Self-assembly of block copolymers." Chemical Society Reviews 41, no. 18 (2012): 5969. http://dx.doi.org/10.1039/c2cs35115c.

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Otsuka, Hidenori, Yukio Nagasaki, and Kazunori Kataoka. "Self-assembly of block copolymers." Materials Today 4, no. 3 (2001): 30–36. http://dx.doi.org/10.1016/s1369-7021(01)80036-5.

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Matsen, Mark W., and Michael Schick. "Self-assembly of block copolymers." Current Opinion in Colloid & Interface Science 1, no. 3 (1996): 329–36. http://dx.doi.org/10.1016/s1359-0294(96)80128-2.

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Noolandi, Jaan, and An-Chang Shi. "Self-assembly of block copolymers." Current Opinion in Colloid & Interface Science 3, no. 4 (1998): 436–39. http://dx.doi.org/10.1016/s1359-0294(98)80062-9.

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SHAO, XI, KAI YANG, and YU-QIANG MA. "A DISSIPATIVE PARTICLE DYNAMICS STUDY ON THE MORPHOLOGIES OF H-SHAPED BLOCK COPOLYMERS IN SOLVENT." International Journal of Modern Physics B 25, no. 06 (2011): 843–50. http://dx.doi.org/10.1142/s0217979211100709.

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Multicompartment micelles have advanced applications in biological and pharmaceutical fields. The self-assembly of the block copolymers with different chain architectures provides versatile and powerful routes to obtain multicompartment micelles in water. Here we apply the dissipative particle dynamics method to study the self-assembly of H-shaped triblock copolymers in a selective solvent. It is found that the H-shaped triblock copolymers can form micelles with different morphologies, such as worm-like micelles, hamburger micelles, core-shell-corona micelles, and cylinder micelles, etc. Among them, the cylinder micelles have not been reported before in the case of the copolymers with similar chain architecture (e.g., Y-shaped copolymer). We demonstrate a convenient approach to obtain different morphologies by only adjusting the arrangement of the copolymers' blocks. These results may be helpful for the design of multicompartment micelles for various application purposes.

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Pandav, Gunja, William J. Durand, Christopher J. Ellison, C. Grant Willson, and Venkat Ganesan. "Directed self assembly of block copolymers using chemical patterns with sidewall guiding lines, backfilled with random copolymer brushes." Soft Matter 11, no. 47 (2015): 9107–14. http://dx.doi.org/10.1039/c5sm01951f.

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Directed self-assembly of block copolymers on chemical patterns with sidewall guiding lines is examined as a function of backfill brush properties, block copolymer film thickness, pattern size, and sidewall interaction strength.

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Folgado, Enrique, Matthias Mayor, Vincent Ladmiral, and Mona Semsarilar. "Evaluation of Self-Assembly Pathways to Control Crystallization-Driven Self-Assembly of a Semicrystalline P(VDF-co-HFP)-b-PEG-b-P(VDF-co-HFP) Triblock Copolymer." Molecules 25, no. 17 (2020): 4033. http://dx.doi.org/10.3390/molecules25174033.

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To date, amphiphilic block copolymers (BCPs) containing poly(vinylidene fluoride-co-hexafluoropropene) (P(VDF-co-HFP)) copolymers are rare. At moderate content of HFP, this fluorocopolymer remains semicrystalline and is able to crystallize. Amphiphilic BCPs, containing a P(VDF-co-HFP) segment could, thus be appealing for the preparation of self-assembled block copolymer morphologies through crystallization-driven self-assembly (CDSA) in selective solvents. Here the synthesis, characterization by 1H and 19F NMR spectroscopies, GPC, TGA, DSC, and XRD; and the self-assembly behavior of a P(VDF-co-HFP)-b-PEG-b-P(VDF-co-HFP) triblock copolymer were studied. The well-defined ABA amphiphilic fluorinated triblock copolymer was self-assembled into nano-objects by varying a series of key parameters such as the solvent and the non -solvent, the self-assembly protocols, and the temperature. A large range of morphologies such as spherical, square, rectangular, fiber-like, and platelet structures with sizes ranging from a few nanometers to micrometers was obtained depending on the self-assembly protocols and solvents systems used. The temperature-induced crystallization-driven self-assembly (TI-CDSA) protocol allowed some control over the shape and size of some of the morphologies.

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Zhou, Yong, and Bing Liu. "Synthesis and Self-Assembly Behavior of Chiral Amphiphilic Diblock Copolymers Bearing L-Phenylalanine." Advanced Materials Research 345 (September 2011): 334–37. http://dx.doi.org/10.4028/www.scientific.net/amr.345.334.

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Novel chiral amphiphilic diblock copolymers bearing L-phenylalanine was synthesized using a “click” reaction of N3-L-phenylalanine and MPEO-b-PGPE. The structure and composition of copolymers were characterized by 1H-NMR and elemental analysis. Additionally, the self-assembly behavior of these chiral copolymers was investigated in sodium dihydrogen phosphate buffer (pH 4.5): the CMC of copolymer MPEO-b-PGTP determined by the measurement of surface tension was 2.1 mg/mL; the size and morphology of the micelles were studied using TEM; the specific optical rotation ([α]25D) of the micellar solutions was also measured; the result indicated that the copolymers can form chiral micelles in sodium dihydrogen phosphate buffer (pH =4.5).In recent years, the synthesis, structure and properties of optically active polymer have been paid attention by scientists owing to its potential applications in chiral separation, asymmetric adsorption, chiral synthesis[1]. The amphiphilic block polymers bearing amino acid possess not only the characteristics of the conventional amphiphilic block copolymer, but also good optically activity and biocompatibility. So it can be employed as nanoreactors for asymmetrical catalysis and materials for drug delivery. But there have been few reports published on the synthesis of chiral amphiphilic copolymers bearing amino acid. Sutthira Sutthasupa reported the synthesis of amino acid-based norbornene block copolymer with ester and carboxyl groups as hydrophobic and hydrophilic units[2]. O’Reilly group synthesized the amino acid-based chiral amphiphilic block copolymers using RAFT technique, and elucidated its self-assembly into spherical micelles with optically active hydrophobic core[3]. In the present work, chiral amphiphilic diblock copolymers bearing L-phenylalanine (L-Phe) pendants poly(ethylene oxide)-b-poly (glycidyl triazolyl-L-phenylalanine) (MPEO-b-PGTP) have been synthesized by the modification of poly(ethylene oxide)-b-poly (propargyl glycidyl ether) (MPEO-b-PGPE) with L-phenylalanine.

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Jang, Jong Dae, Young-Jin Yoon, Sang-Woo Jeon, Young Soo Han, and Tae-Hwan Kim. "Molecular Weight-Dependent, Flexible Phase Behaviors of Amphiphilic Block Copolymer/Additive Complexes in Aqueous Solution." Polymers 13, no. 2 (2021): 178. http://dx.doi.org/10.3390/polym13020178.

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Pluronic amphiphilic block copolymers, well known to have a phase behavior can be controlled by external conditions, have a wide range of potential for applications such as nanotemplates or nanobuilding blocks. However, the phase behaviors of Pluronic block copolymer/additive complexes with highly ordered phases have not been fully investigated. Here, we report the unusual molecular weight-dependent self-assembly of Pluronic block copolymer/additive complexes. Depending on the temperature and additive, Pluronic P65 block copolymer with a lower molecular weight showed the closed loop-like (CLL) phase behavior with the disorder-order-disorder-order phase transition in aqueous solution, whereas Pluronic P105 and P85 block copolymers with higher molecular weights underwent highly ordered continuous phase transitions with face centered cubic (FCC), hexagonal, and lamellar phases. It is expected that the specific phase behavior of the block copolymer/additive complex can be applied in optical devices such as nanotemplates or optical sensors for a highly ordered superlattice. Furthermore, this study provides a new route to control the phase behavior of the block copolymers without a complicated process.

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Serkhacheva, Natalia S., Nickolay I. Prokopov, Evgenii A. Lysenko, Elena Yu Kozhunova, and Elena V. Chernikova. "Modern Trends in Polymerization-Induced Self-Assembly." Polymers 16, no. 10 (2024): 1408. http://dx.doi.org/10.3390/polym16101408.

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Polymerization-induced self-assembly (PISA) is a powerful and versatile technique for producing colloidal dispersions of block copolymer particles with desired morphologies. Currently, PISA can be carried out in various media, over a wide range of temperatures, and using different mechanisms. This method enables the production of biodegradable objects and particles with various functionalities and stimuli sensitivity. Consequently, PISA offers a broad spectrum of potential commercial applications. The aim of this review is to provide an overview of the current state of rational synthesis of block copolymer particles with diverse morphologies using various PISA techniques and mechanisms. The discussion begins with an examination of the main thermodynamic, kinetic, and structural aspects of block copolymer micellization, followed by an exploration of the key principles of PISA in the formation of gradient and block copolymers. The review also delves into the main mechanisms of PISA implementation and the principles governing particle morphology. Finally, the potential future developments in PISA are considered.

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Tang, Xin De, and Jing Xu. "Self-Assembly of ABC-Type Amphiphilic Fluorinated Triblock Copolymers in Different Mixed Solutions." Materials Science Forum 663-665 (November 2010): 880–82. http://dx.doi.org/10.4028/www.scientific.net/msf.663-665.880.

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The behavior of amphiphilic block copolymers in solution has attracted considerable attention in recent years. In this paper, the self-assembly behaviors of the amphiphilic fluorinated ABC-type triblock copolymer (MeOPEO16-PSt220-PFHEA22) in different mixed solutions were studied. Also, the effect of ionic concentration on the self-assembly aggregates of the copolymer in toluene-ethanol-water was studied.

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SUN, PINGCHUAN, YUHUA YIN, BAOHUI LI, QINGHUA JIN, and DATONG DING. "MONTE CARLO SIMULATION OF SELF-ASSEMBLED AMPHIPHILIC DIBLOCK COPOLYMER IN SOLUTION." International Journal of Modern Physics B 17, no. 01n02 (2003): 241–44. http://dx.doi.org/10.1142/s0217979203017424.

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In this paper, Monte Carlo method is applied to simulate the process of the self-assembly of amphiphilic diblock copolymer with a series of block lengths of the insoluble and soluble blocks. Under the given simulation conditions, the diblock copolymers form spherical micelles in solution. The dependence of the core radii of spherical micelles on both block lengths is obtained and compared with experimental results of Eisenberg and coworkers.

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Wan, Lei, Ricardo Ruiz, He Gao, and Thomas R. Albrecht. "Self-Registered Self-Assembly of Block Copolymers." ACS Nano 11, no. 8 (2017): 7666–73. http://dx.doi.org/10.1021/acsnano.7b03284.

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Beránek, Pavel, Paola Posocco, and Zbyšek Posel. "Phase Behavior of Gradient Copolymer Melts with Different Gradient Strengths Revealed by Mesoscale Simulations." Polymers 12, no. 11 (2020): 2462. http://dx.doi.org/10.3390/polym12112462.

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Design and preparation of functional nanomaterials with specific properties requires precise control over their microscopic structure. A prototypical example is the self-assembly of diblock copolymers, which generate highly ordered structures controlled by three parameters: the chemical incompatibility between blocks, block size ratio and chain length. Recent advances in polymer synthesis have allowed for the preparation of gradient copolymers with controlled sequence chemistry, thus providing additional parameters to tailor their assembly. These are polydisperse monomer sequence, block size distribution and gradient strength. Here, we employ dissipative particle dynamics to describe the self-assembly of gradient copolymer melts with strong, intermediate, and weak gradient strength and compare their phase behavior to that of corresponding diblock copolymers. Gradient melts behave similarly when copolymers with a strong gradient are considered. Decreasing the gradient strength leads to the widening of the gyroid phase window, at the expense of cylindrical domains, and a remarkable extension of the lamellar phase. Finally, we show that weak gradient strength enhances chain packing in gyroid structures much more than in lamellar and cylindrical morphologies. Importantly, this work also provides a link between gradient copolymers morphology and parameters such as chemical incompatibility, chain length and monomer sequence as support for the rational design of these nanomaterials.

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Vazaios, Aggelos, Athanasios Touris, Mikel Echeverria, Georgia Zorba, and Marinos Pitsikalis. "Micellization Behaviour of Linear and Nonlinear Block Copolymers Based on Poly(n-hexyl isocyanate) in Selective Solvents." Polymers 12, no. 8 (2020): 1678. http://dx.doi.org/10.3390/polym12081678.

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Block copolymers have attracted significant scientific and economic interest over the last decades due to their ability to self-assemble into ordered structures both in bulk and in selective solvents. In this work, the self-assembly behaviour of both linear (diblocks, triblocks and pentablocks) and nonlinear (miktoarm stars and a block-graft) copolymers based on poly(n-hexyl isocyanate), PHIC, were studied in selective solvents such as n-heptane and n-dodecane. A variety of experimental techniques, namely static and dynamic light scattering, dilute solution viscometry and atomic force microscopy, were employed to study the micellar structural parameters (e.g., aggregation number, overall micellar size and shape, and core and shell dimensions). The effect of the macromolecular architecture, the molecular weight and the copolymer composition on the self-assembly behaviour was studied. Spherical micelles in equilibrium with clusters were obtained from the block copolymers. Thermally stable, uniform and spherical aggregates were found from the triblock copolymers. The poly(n-hexyl isocyanate)-b-polyisoprene-b-poly(n-hexyl isocyanate),-HIH copolymers tend to adopt closed loop conformation, leading to more elongated cylindrical-type structures upon increasing the concentration. Clustering effects were also reported in the case of the pentablock terpolymers. The topology of the blocks plays an important role, since the poly(n-hexyl isocyanate)-b-polystyrene-b-polyisoprene-b-polystyrene-b-poly(n-hexyl isocyanate), HSISH terpolymer shows intermicellar fusion of spherical micelles, leading to the formation of extended networks. The formation of spherical micelles in equilibrium with clusters was obvious in the case of the miktoarm stars, whereas the block-graft copolymer shows the existence of mainly unimolecular micelles.

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Cao, Yong Zhi, Shen Dong, Ying Chun Liang, Tao Sun, and Yong Da Yan. "Block Copolymer Films Hierarchical Assembly in Confinement." Key Engineering Materials 364-366 (December 2007): 437–41. http://dx.doi.org/10.4028/www.scientific.net/kem.364-366.437.

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Ultrathin block copolymer films are promising candidates for bottom-up nanotemplates in hybrid organic-inorganic electronic, optical, and magnetic devices. Key to many future applications is the long range ordering and precise placement of the phase-separated nanoscale domains. In this paper, a combined top-down/bottom-up hierarchical approach is presented on how to fabricate massive arrays of aligned nanoscale domains by means of the self-assembly of asymmetric poly (styrene-block-ethylene/butylenes-block-styrene) (SEBS) tirblock copolymers in confinement. The periodic arrays of the poly domains were orientated via the introduction of AFM micromachining technique as a tool for locally controlling the self-assembly process of triblock copolymers by the topography of the silicon nitride substrate. Using the controlled movement of 2- dimensional precision stage and the micro pressure force between the tip and the surface by computer control system, an artificial topographic pattern on the substrate can be fabricated precisely. Coupled with solvent annealing technique to direct the assembly of block copolymer, this method provides new routes for fabricating ordered nanostructure. This graphoepitaxial methodology can be exploited in hybrid hard/soft condensed matter systems for a variety of applications. Moreover, Pairing top-down and bottom-up techniques is a promising, and perhaps necessary, bridge between the parallel self-assembly of molecules and the structural control of current technology.

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Yue, Xuan, Zhen Geng, Nan Yan, and Wei Jiang. "Hierarchical self-assembly of a PS-b-P4VP/PS-b-PNIPAM mixture into multicompartment micelles and their response to two-dimensional confinement." Physical Chemistry Chemical Physics 22, no. 3 (2020): 1194–203. http://dx.doi.org/10.1039/c9cp05180e.

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Finely tuned synergistic effects among different blocks could realize intriguing hierarchical self-assembly of block copolymers and such hierarchical self-assembly could be manipulated by cylindrical confinement to tune the structures of assemblies.

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Stefik, Morgan, Stefan Guldin, Silvia Vignolini, Ulrich Wiesner, and Ullrich Steiner. "Block copolymer self-assembly for nanophotonics." Chemical Society Reviews 44, no. 15 (2015): 5076–91. http://dx.doi.org/10.1039/c4cs00517a.

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Patel, Dhruvi, Ketan Kuperkar, Shin-ichi Yusa, and Pratap Bahadur. "Nanoscale Self-Assemblies from Amphiphilic Block Copolymers as Proficient Templates in Drug Delivery." Drugs and Drug Candidates 2, no. 4 (2023): 898–922. http://dx.doi.org/10.3390/ddc2040045.

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This review article emphasizes the current enlargements in the formation and properties of the various nanostructured aggregates resulting from the self-assembly of a variety of block copolymers (BCPs) in an aqueous solution. The development of the different polymerization techniques which produce polymers with a desired predetermined molecular weight and low polydispersity is investigated with regard to their technological and biomedical applications; in particular, their applications as vehicles for drug delivery systems are considered. The solution behavior of amphiphilic BCPs and double-hydrophilic block copolymers (DHBCs), with one or both blocks being responsive to any stimulus, is discussed. Polyion complex micelles (PICMs)/polymersomes obtained from the electrostatic interaction of a polyelectrolyte-neutral BCP with oppositely charged species are also detailed. Lastly, polymerization-induced self-assembly (PISA), which forms nanoscale micellar aggregates with controlled size/shape/surface functionality, and the crystallization-driven self-assembly of semicrystalline BCPs facilitated when one block of the BCP is crystallizable, are also revealed. The scalability of the copolymeric micelles in the drug delivery systems and pharmaceutical formations that are currently being used in clinical trials, research, or preclinical testing is emphasized as these micelles could be used in the future to create novel nanomedicines. The updated literature and the future perspectives of BCP self-assembly are considered.

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Zhang, Wei. "Discrete Block Copolymers for Self-Assembly." ACS Central Science 6, no. 8 (2020): 1278–80. http://dx.doi.org/10.1021/acscentsci.0c00913.

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Takenaka, Mikihito, and Hirokazu Hasegawa. "Directed self-assembly of block copolymers." Current Opinion in Chemical Engineering 2, no. 1 (2013): 88–94. http://dx.doi.org/10.1016/j.coche.2012.10.008.

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Zhang, Yuan, Peng Wang, Nan Li, Chunyan Guo, and Sumin Li. "The Effect of Topology on Block Copolymer Nanoparticles: Linear versus Star Block Copolymers in Toluene." Polymers 14, no. 17 (2022): 3691. http://dx.doi.org/10.3390/polym14173691.

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Linear and star block copolymer (BCP) nanoparticles of (polystyrene-block-poly(4-vinylpyridine))n (PS-b-P4VP)n with arm numbers of 1, 2, 3, and 4 were prepared by two methods of polymerization-induced self-assembly (PISA) and general self-assembly of block copolymers in the low-polar organic solvent, toluene. The effect of the arm number on the size and/or morphology of the (PS-b-P4VP)n nanoassemblies synthesized by the two methods in toluene and on the polymerization kinetics was investigated in detail. Our results show that in toluene, a low-polar solvent, the topology not only affected the morphology of the BCP nanoparticles prepared by PISA, but also influenced the BCP nanoparticles synthesized through general self-assembly.

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Martínez-Arranz, Sheila, David Presa-Soto, Gabino A. Carriedo, Alejandro Presa Soto, and Ana C. Albéniz. "Polyphosphazenes for the Stille reaction: a new type of recyclable stannyl reagent." Dalton Transactions 45, no. 5 (2016): 2227–36. http://dx.doi.org/10.1039/c5dt02670a.

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Random and block phosphazene copolymers with stannyl groups have been used as recyclable tin reagents in the Stille reaction. The block copolymer can be recycled without significant release of tin, but its efficiency decreased after three cycles, an effect related to the self-assembly of the polymer.

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Lang, Chao, Manish Kumar, and Robert J. Hickey. "Influence of block sequence on the colloidal self-assembly of poly(norbornene)-block-poly(ethylene oxide) amphiphilic block polymers using rapid injection processing." Polymer Chemistry 11, no. 2 (2020): 375–84. http://dx.doi.org/10.1039/c9py00954j.

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Wang, Huiqi, and Aman Ullah. "Synthesis and Evaluation of Thermoresponsive Renewable Lipid-Based Block Copolymers for Drug Delivery." Polymers 14, no. 17 (2022): 3436. http://dx.doi.org/10.3390/polym14173436.

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Polymeric micelle forming from self-assembly of amphiphilic macromolecules is one of the most potent drug delivery systems. Fatty acids, naturally occurring hydrophobic lipid components, can be considered as potential candidates for the fabrication of block copolymer micelles. However, examples of synthesis of responsive block copolymers using renewable fatty acids are scarce. Herein, we report the synthesis, characterization and testing of block copolymer micelles composed of a renewable fatty-acid-based hydrophobic block and thermoresponsive hydrophilic block for controlled drug delivery. The block copolymers of functionalized fatty acid and poly(N-isopropylacrylamide) (PNIPAM) were prepared via consecutive microwave-assisted reversible addition fragmentation chain transfer (RAFT) polymerization. The block copolymers with variable hydrophobic block length self-assembled in aqueous media and formed spherical nanoparticles of ~30 nm with low critical micelle concentration (CMC). To demonstrate the proof-of-concept, carbamazepine (CBZ) was used as a hydrophobic model drug to evaluate the performance of these micelles as nanocarriers. The in vitro drug release tests were carried out below (25 °C) and above (37 °C) the lower critical solution temperature (LCST) of the block copolymer. The drug release showed obvious temperature-triggered response and an accelerated drug release at 37 °C.

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Evangelio, Laura, Federico Gramazio, Matteo Lorenzoni, et al. "Identifying the nature of surface chemical modification for directed self-assembly of block copolymers." Beilstein Journal of Nanotechnology 8 (September 21, 2017): 1972–81. http://dx.doi.org/10.3762/bjnano.8.198.

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In recent years, block copolymer lithography has emerged as a viable alternative technology for advanced lithography. In chemical-epitaxy-directed self-assembly, the interfacial energy between the substrate and each block copolymer domain plays a key role on the final ordering. Here, we focus on the experimental characterization of the chemical interactions that occur at the interface built between different chemical guiding patterns and the domains of the block copolymers. We have chosen hard X-ray high kinetic energy photoelectron spectroscopy as an exploration technique because it provides information on the electronic structure of buried interfaces. The outcome of the characterization sheds light onto key aspects of directed self-assembly: grafted brush layer, chemical pattern creation and brush/block co-polymer interface.

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Lazzari, Massimo, and Mercedes Torneiro. "A Global View on Block Copolymers." Polymers 12, no. 4 (2020): 869. http://dx.doi.org/10.3390/polym12040869.

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In this systematic review, a total of 45,143 publications on block copolymers, issued between 1952 and 2019, are analyzed in terms of number, source, language, institution, country, keywords, and block copolymer type, to find out their evolution and predict research trends. The number of publications devoted to block copolymers has been growing for over six decades, maintaining a consistent level throughout the last few years. In their majority, documents came out of the United States, although more recently, Chinese institutions are those displaying the largest production. Keywords analysis indicated that one-third of the publications concerned synthesis, around 20% explored self-assembly and morphological aspects, and another 20% referred to block copolymer applications in solution. In particular, 2019 confirmed the expansion of studies related to drug delivery, and in minor extent, to a deeper view of self-assembling. Styrene–butadiene–styrene block copolymer was the most popular in studies covering both basic and industrially oriented aspects. Other highly investigated copolymers are PEO-b–PPO-b–PEO (Pluronic©) and amphiphilic block copolymers based on polycaprolactone or poly(lactic acid), which owed their success to their potential as delivery vehicles. Future trending topics will concern nanomedicine challenges and technology-related applications, with a special attention toward the orientation and ordering of mesophase-separated morphologies.

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Yao, Helen, Kai Sheng, Jialing Sun, et al. "Secondary structure drives self-assembly in weakly segregated globular protein–rod block copolymers." Polymer Chemistry 11, no. 17 (2020): 3032–45. http://dx.doi.org/10.1039/c9py01680e.

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Imparting secondary structure to the polymer block can drive self-assembly in globular protein–helix block copolymers, increasing the effective segregation strength between blocks with weak or no repulsion.

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Aimi, Junko, Motonori Komura, Tomokazu Iyoda, et al. "Synthesis and self-assembly of phthalocyanine-tethered block copolymers." Journal of Materials Chemistry C 3, no. 11 (2015): 2484–90. http://dx.doi.org/10.1039/c4tc02778g.

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Novel block copolymers bearing a phthalocyanine were synthesized via atom transfer radical polymerization and “click” chemistry. Self-assembled nanoarchitectures are obtained through microphase separation of the block copolymers and phthalocyanine π–π interactions.

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Yang, Qin. "Microstructure similarity analysis between synthetic phase-separated block copolymers and natural spider silk." Applied and Computational Engineering 7, no. 1 (2023): 85–93. http://dx.doi.org/10.54254/2755-2721/7/20230357.

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This papers primary purpose is to explore why the microstructure of synthetic block copolymers and natural spider silk is similar at the nanoscale. This paper analyses the main chain segments and secondary structures of natural spider silk, clarifies the aggregation order, and introduces the contribution of secondary systems to the properties of natural block copolymers. Secondly, combined with the synthesis mechanism of natural spider silk, this paper summarizes and analyzes the general process of the synthesized block copolymer. Finally, the conditions of self-assembly of artificial fragments to form the structure are analyzed by employing mean-field theory and a phase diagram. Natural and ideal synthetic spider silk block copolymers have high similarity in performance. To achieve this, scientists can only start from the primary segment to understand their arrangement order in the secondary structure. Then the influence of each block on the properties of the silk fiber is analyzed. At the same time, the size and shape of self-assembled block copolymers are controlled at the micro-scale, thereby changing their properties. The mechanism above shows that the synthesized spider silk block copolymer is similar to natural spider silk in microscopic morphology.

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Jang, Jong Dae, Changwoo Do, Joona Bang, Young Soo Han, and Tae-Hwan Kim. "Self-Assembly of Temperature Sensitive Unilamellar Vesicles by a Blend of Block Copolymers in Aqueous Solution." Polymers 11, no. 1 (2019): 63. http://dx.doi.org/10.3390/polym11010063.

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A self-assembled unilamellar vesicle, which can be used as a drug delivery system, was easily and simply fabricated using a blended system of Pluronic block copolymers. Controlling the hydrophilic mass fraction of block copolymers (by blending the block copolymer with a different hydrophilic mass fraction) and temperature (i.e., the hydrophobic interaction is controlled), a vesicular structure was formed. Small angle neutron scattering measurements showed that the vesicular structure had diameters of empty cores from 13.6 nm to 79.6 nm, and thicknesses of the bilayers from 2.2 nm to 8.7 nm when the hydrophobic interaction was changed. Therefore, considering that the temperature of the vesicle formation is controllable by the concentration of the blended block copolymers, it is possible for them to be applied in a wide range of potential applications, for example, as nanoreactors and nanovehicles.

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Panakkal, Vyshakh M., Dominik Havlicek, Ewa Pavlova, Klara Jirakova, Daniel Jirak, and Ondrej Sedlacek. "Single-Step Synthesis of Highly Sensitive 19F MRI Tracers by Gradient Copolymerization-Induced Self-Assembly." Biomacromolecules 25, no. 12 (2024): 7543–8068. https://doi.org/10.1021/acs.biomac.4c00915.

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Amphiphilic gradient copolymers are promising alternatives to block copolymers for self-assembled nanomaterials due to their straightforward synthesis via statistical copolymerization of monomers with different reactivities and hydrophilicity. By carefully selecting monomers, nanoparticles can be synthesized in a single step through gradient copolymerization-induced self-assembly (gPISA). We synthesized highly sensitive 19F MRI nanotracers via aqueous dispersion gPISA of hydrophilic poly(ethylene glycol) methyl ether methacrylate (PEGMA) with core-forming N,N-(2,2,2-trifluoroethyl)acrylamide (TFEAM). The PPEGMA-grad-PTFEAM nanoparticles were optimized to achieve spherical morphology and exceptional 19F MRI performance. Noncytotoxicity was confirmed in Panc-1 cells. In vitro 19F MR relaxometry and imaging demonstrated their diagnostic imaging potential. Notably, these gradient copolymer nanotracers outperformed block copolymer analogs in 19F MRI performance due to their gradient architecture, enhancing 19F relaxivity. The synthetic versatility and superior 19F MRI performance of gradient copolymers highlight their potential in advanced diagnostic imaging applications.

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Zhang, Keren, Gregory B. Fahs, Motohiro Aiba, Robert B. Moore, and Timothy E. Long. "Nucleobase-functionalized ABC triblock copolymers: self-assembly of supramolecular architectures." Chem. Commun. 50, no. 65 (2014): 9145–48. http://dx.doi.org/10.1039/c4cc03363a.

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Gadzinowski, Mariusz, Maciej Kasprów, Teresa Basinska, et al. "Synthesis, Hydrophilicity and Micellization of Coil-Brush Polystyrene-b-(polyglycidol-g-polyglycidol) Copolymer—Comparison with Linear Polystyrene-b-polyglycidol." Polymers 14, no. 2 (2022): 253. http://dx.doi.org/10.3390/polym14020253.

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In this paper, an original method of synthesis of Coil-Brush amphiphilic polystyrene-b-(polyglycidol-g-polyglycidol) (PS-b-(PGL-g-PGL)) block copolymers was developed. The hypothesis that their hydrophilicity and micellization can be controlled by polyglycidol blocks architecture was verified. The research enabled comparison of behavior in water of PS-b-PGL copolymers and block–brush copolymers PS-b-(PGL-g-PGL) with similar composition. The Coil-Brush copolymers were composed of PS-b-PGL linear core with average DPn of polystyrene 29 and 13 of polyglycidol blocks. The DPn of polyglycidol side blocks of coil–b–brush copolymers were 2, 7, and 11, respectively. The copolymers were characterized by 1H and 13C NMR, GPC, and FTIR methods. The hydrophilicity of films from the linear and Coil-Brush copolymers was determined by water contact angle measurements in static conditions. The behavior of Coil-Brush copolymers in water and their critical micellization concentration (CMC) were determined by UV-VIS using 1,6-diphenylhexa-1,3,5-trien (DPH) as marker and by DLS. The CMC values for brush copolymers were much higher than for linear species with similar PGL content. The results of the copolymer film wettability and the copolymer self-assembly studies were related to fraction of hydrophilic polyglycidol. The CMC for both types of polymers increased exponentially with increasing content of polyglycidol.

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Hicks, Garion E. J., Charles N. Jarrett-Wilkins, Jenny R. Panchuk, Joseph G. Manion та Dwight S. Seferos. "Oxidation promoted self-assembly of π-conjugated polymers". Chemical Science 11, № 25 (2020): 6383–92. http://dx.doi.org/10.1039/d0sc00806k.

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Yu, Xiaoqian, Artjom Herberg, and Dirk Kuckling. "Micellar Organocatalysis Using Smart Polymer Supports: Influence of Thermoresponsive Self-Assembly on Catalytic Activity." Polymers 12, no. 10 (2020): 2265. http://dx.doi.org/10.3390/polym12102265.

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Micellar catalysts with a switchable core are attractive materials in organic synthesis. However, little is known about the role of the shell forming block on the performance of the catalyst. Thermoresponsive block copolymers based on poly(N-isopropylacrylamide-co-vinyl-4,4-dimethylazlactone) attached to different permanently hydrophilic blocks, namely poly(ethylene glycol), poly(N,N-dimethylacrylamide), and poly(2,3-dihydroxypropyl acrylate), were successfully synthesized via reversible addition/fragmentation chain transfer radical polymerization (RAFT). Post-polymerization attachment of an amino-functionalized L-prolineamide using the azlactone ring-opening reaction afforded functionalized thermoresponsive block copolymers. Temperature-induced aggregation of the functionalized block copolymers was studied using dynamic light scattering. It was shown that the chemical structure of the permanently hydrophilic block significantly affected the size of the polymer self-assemblies. The functionalized block copolymers were subjected to an aldol reaction between p-nitrobenzaldehyde and cyclohexanone in water. Upon temperature-induced aggregation, an increase in conversion was observed. The enantioselectivity of the polymer-bound organocatalyst improved with an increasing hydrophilic/hydrophobic interface as a result of the different stability of the polymer aggregates.

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Kim, Chan-Jin, Eun Hye Jeong, Hyukjin Lee, and So-Jung Park. "A dynamic DNA nanostructure with switchable and size-selective molecular recognition properties." Nanoscale 11, no. 5 (2019): 2501–9. http://dx.doi.org/10.1039/c8nr09341e.

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Binary self-assembly of DNA block copolymers and thermo-responsive block copolymers generated dynamic DNA nanostructures with unique capabilities to selectively block or unblock interactions with proteins and cells.

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Vora, Ankit, Rudy J. Wojtecki, Kristin Schmidt, et al. "Development of polycarbonate-containing block copolymers for thin film self-assembly applications." Polymer Chemistry 7, no. 4 (2016): 940–50. http://dx.doi.org/10.1039/c5py01846c.

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Bai, Yizhe. "Application of self-assembly technology in the field of medicine." Applied and Computational Engineering 7, no. 1 (2023): 104–12. http://dx.doi.org/10.54254/2755-2721/7/20230375.

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In recent years, the preparation of polymer micelles and self-assembled nanomaterials by amphiphilic block copolymers has attracted great interest and has now become a research hotspot in the field of polymer science. Based on the self-assembly technology of block compounds, this paper introduces how self-assembly technology can play a role in the clinical environment, especially for the treatment of tumors and cancer, and controlled drug release. Finally, the related challenges and opportunities for self-assembled nanoparticles are described and prospected. Currently, although block copolymers have great performance in many fields, it is difficult to summarize one or a series of regular methods for the preparation of block copolymers and we also did not find a preparation method suitable for industrial production and wide application.

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