Article
Polymer Science
Andrew Selkirk, Nadezda Prochukhan, Ross Lundy, Cian Cummins, Riley Gatensby, Rachel Kilbride, Andrew Parnell, Jhonattan Baez Vasquez, Michael Morris, Parvaneh Mokarian-Tabari
Summary: This study overcomes the kinetic challenges in the self-assembly of UHMW BCPs through precision solvent annealing, resulting in highly ordered large-period lamellar domains. The research reveals that film thickness and solvent concentration significantly affect the domain morphology.
Article
Chemistry, Multidisciplinary
Hongyun Xu, Han Xiao, Christopher J. Ellison, Mahesh K. Mahanthappa
Summary: This study successfully synthesized materials with nanoporous structures through thermal cross-linking and selective chemical etching, challenging the expectation that remaining cylinders cannot form a continuous material. Scanning electron microscopy imaging revealed the interconnected nanostructures, while permeation behavior of poly(ethylene oxide) based on hydrodynamic radius directly demonstrated the continuity and size selectivity of the material.
Article
Chemistry, Physical
Rasha Ahmed Hanafy Bayomi, Takashi Aoki, Sono Sasaki, Shinichi Sakurai
Summary: This study reports the spontaneous dewetting of a sphere-forming block copolymer film and the formation of plateau-shaped islands with regularly ordered spherical microdomains. The degree of deformation of the hexagonal lattice in the dewetted islands increases with the degree of island shape deformation, leading to well-ordered arrangement of microdomains. However, the regular ordering is disrupted near the edges of the islands due to mismatch between the island's curvature and the ordered grain shape.
Article
Chemistry, Multidisciplinary
Suwon Bae, Kevin G. Yager
Summary: Experimental and simulation studies have shown that the nanoscale morphology of BCP thin films is determined by chain architecture, and blending can stabilize new motifs and lead to the appearance of coexistence phases.
Article
Polymer Science
Haohui Huo, Jie Liu, Senthil Kannan, Long Chen, Yimin Zhao, Lei Zhang, Gang Chang, Qilu Zhang, Feng Liu
Summary: This study presents the first example of protein-like multicompartment nanoparticles formed via self-assembly of a specifically designed 21-arm star polymer, PEG(PAA-b-PS)(20). The morphology of the MCNs is determined by the volume ratio of PS to PAA, and unique string structures composed of one-dimensional alignment of single-star polymers were observed for the first time. A new mechanism for the assembly of star polymers was proposed based on investigations under different conditions, suggesting potential applications in drug delivery and catalysis.
Article
Nanoscience & Nanotechnology
Kshitij Sharma, Aman Agrawal, Ali Masud, Sushil K. Satija, John F. Ankner, Jack F. Douglas, Alamgir Karim
Summary: The kinetics and morphology of block copolymer films are influenced by the processing pathway, which affects the enthalpic and entropic forces driving the ordering processes. Understanding the free energy landscape and how processing procedures can move the system through this landscape is important for controlling the variability of block copolymer morphology. The authors demonstrate a method where a target low-energy structure can be quickly achieved by subjecting as-cast films to initial solvent annealing followed by a short period of thermal annealing.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Materials Science, Multidisciplinary
Sajan Singh, Tandra Ghoshal, Nadezda Prochukhan, Alberto Alvarez Fernandez, Jhonattan Frank Baez Vasquez, Pravind Yadav, Sibu C. Padmanabhan, Michael A. Morris
Summary: In this study, we demonstrated the formation of oxide porous and nanodot structures from the same block copolymer (BCP) through the phase inversion of a BCP template. The effect of solvent annealing time on the ordering of the BCP was investigated. Metal ions were infiltrated into the BCP templates and oxidized to their oxides. The resulting structures were analyzed through various methods, confirming the complete elimination of the BCP template and the presence of metal oxides.
ACS APPLIED POLYMER MATERIALS
(2023)
Article
Chemistry, Physical
Xi Mao, Hao Li, Jinwoo Kim, Shuai Deng, Renhua Deng, Bumjoon J. Kim, Jintao Zhu
Summary: A solvent annealing-induced structural reengineering approach transforms polystyrene-b-poly(4-vinyl pyridine) into polymersomes, allowing for effective encapsulation/loading of cargoes such as fluorescent dyes and metal nanoparticles for various applications.
Editorial Material
Nanoscience & Nanotechnology
Kevin G. Yager
Summary: The self-assembly of a triblock bottlebrush polymer at one length scale determines the organization of the self-assembly at a smaller scale, creating a hierarchical unit cell.
NATURE NANOTECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Bin Zhao, Chao Wang, Yingcai Chen, Meijiao Liu
Summary: In this study, the formation mechanism of complex FK phases from self-assembly of simple A(1)B(1)A(2)B(2) tetrablock copolymers was investigated using SCFT, revealing precise control over the distribution of A(1) and A(2) blocks by tuning the A(1)/A(2) block ratio in stable FK phases. Additionally, the presence of the B-2 block was shown to play a crucial role in stabilizing the FK phases.
Article
Polymer Science
Yu-Hsuan Tseng, Yu-Liang Lin, Jhih-Hao Ho, Chun-Ting Chang, Yi-Chun Fan, Ming-Hui Shen, Jiun-Tai Chen
Summary: This study presents a clever approach to form PS-b-PEO nanorods in nanopores of AAO templates using solvent vapor annealing method, allowing for control over the internal morphologies of the nanorods by changing the annealing solvents. This technique provides a powerful tool for fabricating functional nanomaterials with unique morphologies, showing great potential for various applications.
Article
Polymer Science
Ling-Ying Shi, Zhixiong Fei, Qian Wang, Lin Weng, Chenxiao Yin, Jinrui Sun, Zhihao Shen
Summary: Bottlebrush block copolymers (BBCPs) are intriguing architectural polymers that can produce various anisotropic nanostructures. This study presents a method for creating ordered silicon oxide patterns and particles on substrates using solvent vapor induced thin film self-assembly of BBCPs containing polydimethylsiloxane (PDMS) and polystyrene (PS) side chains. Different morphologies, including cylindrical or stripes-like, spherical, and ordered porous structures, as well as Janus particle-like structures, were achieved through solvent vapor annealing. The Janus particle-like structures were further transformed into meso-to-macroporous silicon oxide bowls after oxygen plasma etching. The study also discussed the effects of solvent vapor and backbone length on the self-assembly behavior of the thin film.
Article
Polymer Science
Timothy P. Lodge, En Wang, Jiahao Zhu, Frank S. Bates
Summary: The self-assembly behavior of four polystyrene and poly(ethylene-alt-propylene) block copolymers in a selective solvent was studied. Spherical micelles were formed by all four polymers, with the symmetric triblock copolymer having the smallest micelle size. However, the asymmetric triblock copolymers did not form any specific packing arrangement. This result suggests that the two-layer corona of the asymmetric triblock copolymers may play a role in their self-assembly behavior. At higher concentrations, all four polymers adopted hexagonal packings before transitioning to lamellar structures.
Article
Polymer Science
Nico Alleva, Katharina Eigen, David Y. W. Ng, Tanja Weil
Summary: We propose a simple and versatile method to purify and isolate DNA-polymer conjugates from various types of uncharged homo, random, or block copolymer families. Anion exchange chromatography is utilized for separation and recovery of excess unreacted polymer and oligonucleotide. With a high yield and efficient purification process, this method demonstrates its broad applicability for different polymer families and DNA block lengths.
Article
Materials Science, Multidisciplinary
Ze Ye, Ze-Kun Zhang, Shi-Peng Ding, Ding-Li Xia, Jun-Ting Xu
Summary: In this study, a block copolymer was used to fabricate electrolytes containing double conductive nanophases. The distribution of lithium salt in the two phases was quantitatively characterized, and it was found that the salt content in the PEO phase is relatively higher. The hybrids with lower doping ratios showed larger grain sizes and smaller interphase thickness, and were more sensitive to temperature changes.
ACS APPLIED POLYMER MATERIALS
(2022)
Article
Multidisciplinary Sciences
Pawel W. Majewski, Aaron Michelson, Marco A. L. Cordeiro, Cheng Tian, Chunli Ma, Kim Kisslinger, Ye Tian, Wenyan Liu, Eric A. Stach, Kevin G. Yager, Oleg Gang
Summary: The rapid development of DNA-based assembly methods allows for the creation of organized nanomaterials with versatile capabilities. By creating inorganic, silica-based replicas of 3D periodic DNA-NP structures, the formed nanomaterials demonstrate excellent resiliency and stability under extreme conditions. This approach opens up new possibilities for the use of DNA assembly strategies in creating organized nanomaterials for a broad range of operational conditions.
Article
Polymer Science
Piotr Cieciorski, Pawel W. Majewski, Elzbieta Megiel
Summary: A series of photoresponsive poly(meth)acrylates containing azobenzene groups were synthesized, showing reversible structural transformation under light illumination and high potential for energy storage applications. The enthalpy determined from DSC was relatively high, indicating liquid-crystalline behavior of the materials.
Correction
Polymer Science
Kristof Toth, Suwon Bae, Chinedum O. Osuji, Kevin G. Yager, Gregory S. Doerk
Article
Polymer Science
Arkadiusz A. Leniart, Przemyslaw Pula, Robert W. Style, Pawel W. Majewski
Summary: The study quantitatively analyzed BCP grain-coarsening in thin films under controlled solvent evaporation and found an exponential dependence on the kinetics power-law time exponent on polymer concentration. This dependence was used to create a mathematical model and coarsening rate diagram for aiding in engineering the BCP processing pathway.
Article
Chemistry, Multidisciplinary
Suwon Bae, Kevin G. Yager
Summary: Experimental and simulation studies have shown that the nanoscale morphology of BCP thin films is determined by chain architecture, and blending can stabilize new motifs and lead to the appearance of coexistence phases.
Article
Chemistry, Multidisciplinary
Hanyu Wu, Hairui Huang, Yizhou Zhang, Xinglin Lu, Pawel W. Majewski, Xunda Feng
Summary: Researchers have successfully stabilized cross-linkable bicontinuous cubic liquid crystal phases and fabricated ordered polymeric materials with 1 nm channels. These materials exhibit the required mechanical integrity and chemical robustness in various organic solvents, making them suitable for practical applications in selective ion and molecule transport.
Editorial Material
Nanoscience & Nanotechnology
Kevin G. Yager
Summary: The self-assembly of a triblock bottlebrush polymer at one length scale determines the organization of the self-assembly at a smaller scale, creating a hierarchical unit cell.
NATURE NANOTECHNOLOGY
(2023)
Article
Multidisciplinary Sciences
Sebastian T. Russell, Suwon Bae, Ashwanth Subramanian, Nikhil Tiwale, Gregory Doerk, Chang-Yong Nam, Masafumi Fukuto, Kevin G. Yager
Summary: This article introduces a method to access new non-equilibrium morphologies using layering assembly. By controlling the initial configuration and ordering history of thin films, as well as thermal annealing for evolution, higher diversity of non-native morphologies can be achieved.
NATURE COMMUNICATIONS
(2022)
Article
Multidisciplinary Sciences
Gregory S. Doerk, Aaron Stein, Suwon Bae, Marcus M. Noack, Masafumi Fukuto, Kevin G. Yager
Summary: In this study, machine-guided discovery of emergent morphologies from a cylinder/lamellae block copolymer blend directed by a chemical grating template was demonstrated without direct human intervention on a synchrotron x-ray scattering beamline. This approach enables mapping of the morphology-template phase space in less time than manual characterization, and highlights regions that warrant further investigation. The results reveal localized, template-directed partitioning of coexisting lamella- and cylinder-like subdomains at the template period length scale, resulting in previously unknown morphologies such as aligned alternating subdomains, bilayers, or a ladder morphology. This work emphasizes the crucial role that autonomous characterization can play in advancing the paradigm of directed self-assembly (DSA).
Review
Nanoscience & Nanotechnology
Kevin G. Yager, Pawel W. Majewski, Marcus M. Noack, Masafumi Fukuto
Summary: Autonomous experimentation is an emerging paradigm that aims to automate the entire experiment workflow, including the decision-making step. By exploiting Gaussian process modeling and objective function, recent progress has been made in the application of this concept at synchrotron x-ray scattering beamlines. The automation of measurement instrument, data analysis, and decision-making, coupled with in situ processing platforms, facilitates efficient exploration of physical spaces and discovery of new materials.
Article
Physics, Multidisciplinary
Jadwiga Szydlowska, Pawel Majewski, Mojca Cepic, Natasa Vaupotic, Paulina Rybak, Corrie T. Imrie, Rebecca Walker, Ewan Cruickshank, John M. D. Storey, Pociecha Damian, Ewa Gorecka
Summary: A critical point was identified in a ferroelectric nematic liquid crystal material where an isotropic phase transforms into a polar nematic phase with increasing electric field. This critical point occurs approximately 30 K above the zero-field transition temperature and at an electric field of around 10 V/μm. Such systems are intriguing for their ability to induce strong birefringence in an optically isotropic phase over a broad temperature range.
PHYSICAL REVIEW LETTERS
(2023)
Article
Nanoscience & Nanotechnology
Przemyslaw Pula, Arkadiusz A. Leniart, Julia Krol, Maciej T. Gorzkowski, Mihai C. Suster, Piotr Wrobel, Adam Lewera, Pawel W. Majewski
Summary: This article reports an economical, time-efficient, and easily scalable method of fabricating transition metal oxide nanowires using simultaneous block copolymer self-assembly and selective sequestration of metal-organic acetylacetonate complexes. The mechanism and primary factors responsible for the sequestration and conformal replication of the polymer template by the inorganic material are discussed. Additionally, the developed fabrication scheme is demonstrated to be capable of patterning multilayered nanomesh and constructing a prototype volatile organic compound sensor.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Physical
Samantha R. Nowak, Nikhil Tiwale, Gregory S. Doerk, Chang-Yong Nam, Charles T. Black, Kevin G. Yager
Summary: Blends of block copolymers are capable of responding to interfacial energy, allowing for the selection of pure or coexisting phases based on surface chemistry. This behavior stabilizes usually metastable structures, resulting in the generation of pure hexagonally perforated lamellar thin films across various thicknesses and surface energies. The responsiveness of the blend materials allows for the spatial definition of morphology through multi-tone chemical surface patterns.
Article
Chemistry, Multidisciplinary
Suwon Bae, Marcus M. Noack, Kevin G. Yager
Summary: This study investigates the ordering of diblock copolymers in thin films using coarse-grained molecular dynamics simulations, focusing on chain makeup, substrate surface energy, and surface tension disparity between the two constituent blocks. A machine-learning approach using a Gaussian process control algorithm is used to explore the parameter space and train a GP model that captures the system response and extracts material knowledge. It is found that the vertical orientation of BCP phases depends on multiple energetic contributions, including entropic and enthalpic material enrichment, distortion of morphological objects, and interfacial energies.
Review
Chemistry, Physical
Przemyslaw Pula, Arkadiusz Leniart, Pawel W. Majewski
Summary: Solvent-assisted block copolymer self-assembly is a promising method for controlling the morphology and ordering kinetics of BCPs, thus advancing their practical applications. However, the development of a universal BCP patterning protocol remains challenging due to various factors influencing the self-assembly scenario. This review aims to summarize the seminal reports and latest progress in solvent-assisted directed self-assembly of BCPs, providing theoretical background and highlighting significant research areas and emerging high-tech applications where solvent-assisted processing could have a dominant role.
Article
Chemistry, Physical
Yiping Yin, Zhe Wang, Hua Zou
Summary: This study presents a novel method for preparing dimpled polymer-silica nanocomposite particles using interfacial swelling-based seeded polymerization. The optimized conditions allow for a relatively high percentage of dimpled particles to be achieved.
Article
Chemistry, Physical
Brenden D. Hoehn, Elizabeth A. Kellstedt, Marc A. Hillmyer
Summary: Porous materials with nanometer-scale pores have important applications as nanoporous membranes. In this study, ABA triblock copolymers were used as precursors to produce nanoporous polymeric membranes (NPMs) in thin film form by degrading the end blocks. Polycyclooctene (PCOE) NPMs with tunable pore sizes were successfully prepared using solvent casting technique. Oxygen plasma etching was employed to improve the surface porosity and hydrophilicity of the membranes. This study provides a straightforward method to produce tough NPMs with high porosity and hydrophilic surface properties.
Article
Chemistry, Physical
Vladislav S. Petrovskii, Stepan I. Zholudev, Igor I. Potemkin
Summary: This article investigates the behavior of linear and ring polypeptide chains in aqueous solution and explores the properties of the complexes formed by these chains with oppositely charged surfactants. The results demonstrate that the complexes of linear supercharged unfolded polypeptides and the corresponding surfactants exhibit impressive adhesive properties.
Article
Chemistry, Physical
Merve Cevik, Serkan Dikici
Summary: Cardiovascular diseases are a leading cause of death globally, and vascular grafts are a promising treatment option. This study focuses on tissue-engineered vascular grafts (TEVGs) using decellularized parsley stems as a potential biomaterial. The decellularized parsley stems showed suitable properties for TEVGs, providing a suitable environment for human endothelial cells to form a pseudo endothelium. This study showcases the potential of using parsley stems for TEVGs.
Article
Chemistry, Physical
Gustavo A. Vasquez-Montoya, Tadej Emersic, Noe Atzin, Antonio Tavera-Vazquez, Ali Mozaffari, Rui Zhang, Orlando Guzman, Alexey Snezhko, Paul F. Nealey, Juan J. de Pablo
Summary: The optical properties of liquid crystals are typically controlled by electric fields. In this study, we investigate the effects of microfluidic flows and acoustic fields on the molecular orientation and optical response of nematic liquid crystals. We identify several previously unknown structures and explain them through calculations and simulations. These findings hold promise for the development of new systems combining sound, flow, and confinement.
Article
Chemistry, Physical
Xinjun Wu, Xin Guan, Shushu Chen, Jiangpeng Jia, Chongyi Chen, Jiawei Zhang, Chuanzhuang Zhao
Summary: This research presents a novel shape memory hydrogel with a remodelable permanent shape and programmable cold-induced shape recovery behavior. The hydrogel is prepared using specific treatment methods to achieve shape fixation by heating and shape recovery by cooling. Additionally, deformable devices can be obtained by assembling hydrogel blocks with different concentrations.
Article
Chemistry, Physical
Rebecca Hengsbach, Gerhard Fink, Ulrich Simon
Summary: This study examines the properties of DNA functionalized pNipmam microgels and pure pNipmam microgels at different concentrations of sodium chloride and in PBS solutions using temperature dependent H-1-NMR measurements. The results show that DNA modification affects the volume phase transition temperature and the addition of salt and PBS further enhances this effect.
Article
Chemistry, Physical
Ningyi Li, Junhong Li, Lijingting Qing, Shicheng Ma, Yao Li, Baohui Li
Summary: This paper investigates the self-assembly behavior of colloids with competing interactions under spherical confinement and finds that different ordered structures can be formed under different sized spherical confinements. Moreover, more perforated structures are formed in smaller spheres.
