Article
Polymer Science
Tomoka Yoshimura, Tomofumi Morishita, Yoshihiro Agata, Kodai Nagashima, Kevin Wylie, Yuta Nabae, Teruaki Hayakawa, Makoto Ouchi
Summary: We achieved long-range ordered lamellar formation in PS-PMMA block copolymers by introducing oligopeptides at the junction. The structure of the oligopeptides determined the formation of a periodic lamellar structure in the block copolymers, with the hexFFFFhex sequence showing the best results.
Article
Polymer Science
Aum Sagar Panda, Yi-Chien Lee, Thanmayee Shastry, Gkreti-Maria Manesi, Apostolos Avgeropoulos, Rong-Ming Ho
Summary: This study demonstrates a simple method to control the orientation of self-assembled nanostructured block copolymer thin films by functionalizing the oxide layer on the substrate and conducting thermal annealing under low-pressure environmental conditions. By grafting hydroxy-terminated polystyrene and polydimethylsiloxane brushes onto the substrate, the affinities of the polymer blocks with the substrate can be fine-tuned to achieve perpendicular cylinder orientation after annealing. The vacuum-driven approach combined with substrate functionalization allows the generation of perpendicular cylinders at both the air/polymer interface and the substrate/polymer interface, leading to the fabrication of well-aligned perpendicular cylinders with long-range ordering.
Article
Materials Science, Multidisciplinary
You Wu, Yin-Ning Zhou, Qun-Jie Xu, Jin-Jin Li, Zheng-Hong Luo
Summary: Two well-defined amphiphilic block copolymers were synthesized through activators regenerated by electron transfer atom transfer radical polymerization, which served as stabilizers for preparing styrene and methyl methacrylate containing HIPEs. The block copolymer stabilized HIPEs and polyHIPEs showed higher strength compared to samples stabilized by span80, with PS-based polyHIPEs having a closed-cell structure and PMMA-based polyHIPEs having an open-cell structure. The concentration of stabilizer played a critical role in preparing high-porosity PMMA-based polyHIPEs. Other functional polymeric porous monoliths can be readily prepared through HIPE templating using commonly known PEO-PS block copolymers.
MATERIALS TODAY COMMUNICATIONS
(2021)
Article
Spectroscopy
Jiho Kim, Wooseop Lee, Hyeji Kim, Du Yeol Ryu, Hyungju Ahn, Boknam Chae
Summary: A non-invasive, image-based analytic method using scattering-type scanning near-field optical microscopy (s-SNOM) is proposed to evaluate the phase separation behavior of lamella-forming polymer films, and the influence of self-assembly processes on the spatial distribution of polymer components is investigated.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2022)
Article
Polymer Science
Fu-Rong Chen, Rong-Ming Ho, Chen-Jung Hung, Aum Sagar Panda, Yi-Chien Lee, Shih-Yi Liu, Jheng-Wei Lin, Hsiao-Fang Wang, Apostolos Avgeropoulos, Fan-Gang Tseng
Summary: In this study, the controlled self-assembly of star-block polystyrene-blockpolydimethylsiloxane (PS-b-PDMS) thin films was directly visualized using in situ transmission electron microscopy (TEM) observations. The self-alignment process of film-spanning perpendicular cylinders in the block copolymer (BCP) thin films was investigated under low-dose conditions using an environmental chip with a built-in microheater. The time-resolved self-alignment process was systematically compared between symmetric and asymmetric conditions, providing comprehensive insights into the nucleation and growth mechanism.
Article
Nanoscience & Nanotechnology
Hongbo Hao, Shuangjun Chen, Jiaxing Ren, Xuanxuan Chen, Paul Nealey
Summary: This study investigated the effect of the ionic liquid HMHF on the line edge roughness of PS-b-PMMA self-assembled patterns and found that a small amount of HMHF can improve the photolithography compatibility of PS-b-PMMA and reduce the LER value.
Article
Polymer Science
Masaki Tamura, Naruki Kurokawa, Atsushi Hotta
Summary: In this study, effective bottlebrush polymers were synthesized to achieve almost zero birefringence when mixed with optical PMMA. By blending different ratios of linear PMMA and PMMA-BBP and subjecting them to uniaxial drawing, the orientation birefringence of PMMA could be effectively controlled and removed.
Article
Polymer Science
Bastian Grabe, Wolf Hiller
Summary: This study presents a new method to determine the molar mass distribution of block copolymers using nuclear magnetic resonance diffusion ordered spectroscopy with inverse Laplace transform. The results show that the DOSY approach, combined with dual detector size exclusion chromatography, accurately determines the molar mass distribution of block copolymers.
Article
Chemistry, Multidisciplinary
Donghwan Kim, Eunchan Kim, Sohyun Park, Seungah Kim, Byoung Koun Min, Hyo Jae Yoon, Kyungwon Kwak, Minhaeng Cho
Summary: The study utilized vibrational sum-frequency-generation spectroscopy to elucidate the water structure at a water-graphene interface. The observation of an excellent correlation between water adhesion energy of graphene and the fraction of dangling OH groups suggests that VSFG can be an incisive technique for measuring water's adhesion energy on spatially confined interfaces. The results are anticipated to aid in understanding the wettability of low-dimensional materials.
Article
Polymer Science
Areen A. Bani-Salameh, A. A. Ahmad, A. M. Alsaad, I. A. Qattan, Ihsan A. Aljarrah
Summary: This study synthesized hybrid thin films based on PMMA and PS doped with different concentrations (1%, 3%, 5%, 7%) of CeO2 NPs. The results indicated that with increasing CeO2 NPs concentration, the optical band gap energy of PMMA-PS/CeO2 NPs thin films decreased significantly, with high transmittance in the low-energy region and a sharp decrease in the high-energy region.
Article
Chemistry, Physical
Prasad Rama, Zareen Abbas
Summary: The role of nanoparticle shape in the interaction and adsorption of organic molecules on the particle surface is explored in this study. The results show that the shape of silica nanoparticles significantly affects the interaction of water molecules, counter-ions, and organic molecules, which consequently determine the adsorption behavior of organic molecules on the nanoparticle surface.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Materials Science, Composites
Hanxiong Lyu, Naiyu Jiang, Yingze Li, Dongxing Zhang
Summary: The interfacial adhesion between carbon fiber (CF) and polyetheretherketone (PEEK) was improved by modifying the interface with hydroxylated PEEK grafted onto multi-walled carbon nanotubes. The modified CFs showed increased surface roughness, more polar groups, decreased contact angle, and increased surface energy, leading to enhanced wettability and improved physical adhesion, resulting in significant enhancements in the mechanical properties of the CF/PEEK composites.
COMPOSITES SCIENCE AND TECHNOLOGY
(2021)
Article
Nanoscience & Nanotechnology
Wei Cao, Shanshan Yin, Martina Plank, Andrei Chumakov, Matthias Opel, Wei Chen, Lucas P. Kreuzer, Julian E. Heger, Markus Gallei, Calvin J. Brett, Matthias Schwartzkopf, Artem A. Eliseev, Evgeny O. Anokhin, Lev A. Trusov, Stephan Roth, Peter Mueller-Buschbaum
Summary: The study focuses on utilizing spray deposition technique to fabricate hybrid films with perpendicular magnetic anisotropy, by controlling the orientation of nanoparticles and polymers, and further tuning their magnetic properties through solvent vapor annealing. The results demonstrate the potential applications of spray-deposited hybrid films in magnetic data storage and sensors.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Multidisciplinary Sciences
Sandeep Kumar, Sunil Kumar
Summary: Ultrafast THz radiation is observed from annealed ferromagnetic/nonmagnetic bilayers, with temperature-dependent emission intensity and polarity. The results highlight the significant contribution of interface modifications to the overall spin-Hall angle.
Article
Chemistry, Physical
Jia-Wen Hong, Jung-Hong Chang, Iris Ching-Ya Chang, Ya-Sen Sun
Summary: By studying the phase behavior of substrate-supported films, we found that different nano-domains appear sequentially with increasing PS content, including lamellae, perforated layers, double gyroid, and cylinders. Annealing temperature and film thickness have significant effects on the formation of perforated layers and double gyroids, with lower annealing temperatures favoring a greater fraction of perforated layers in thick films.
Review
Chemistry, Multidisciplinary
Cheng Zhang, Kai Yan, Changkui Fu, Hui Peng, Craig J. Hawker, Andrew K. Whittaker
Summary: This review discusses the applications of fluorinated molecules in bioengineering and nanotechnology, with a focus on controlling fluorine-fluorine interactions and understanding their impact on biological behavior. The controlled introduction of fluorine and its interactions can provide advantages in imaging, therapeutics, and environmental applications.
Article
Polymer Science
Marcel U. Brown, Hong-Gyu Seong, Khatcher O. Margossian, Lauren Bishop, Thomas P. Russell, Murugappan Muthukumar, Todd Emrick
Summary: Polymer zwitterions have various applications, but the variation in their chemical composition is limited. This article highlights the use of 4-vinylbenzyl sultone as a precursor to ammonium sulfonate zwitterionic monomers, which are then used to synthesize inverted sulfobetaine polymer zwitterions.
MACROMOLECULAR RAPID COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Ganhua Xie, Pei Li, Paul Y. Kim, Pei-Yang Gu, Brett A. Helms, Paul D. Ashby, Lei Jiang, Thomas P. Russell
Summary: Water-walking insects use capillary forces to climb or descend the meniscus between water surface and a solid object by changing body posture, which inspired the development of autonomous aquatic synthetic systems that can shuttle cargo underground between landing and drop-off sites. By controlling the contact angle of a coacervate sac or hydrogel droplet, cyclic cargo shuttling can occur continuously as long as reactants from the surrounding aqueous phase are not depleted, potentially leading to applications in autonomously driven reaction or delivery systems and micro-/milli-robotics.
Article
Chemistry, Multidisciplinary
Seamus D. Jones, Howie Nguyen, Peter M. Richardson, Yan-Qiao Chen, Kira E. Wyckoff, Craig J. Hawker, Raphaele J. Clement, Glenn H. Fredrickson, Rachel A. Segalman
Summary: By self-assembling into superionically conductive domains, the ion electrolyte overcomes the limitation of limited conductivity and achieves excellent performance in lithium-ion batteries.
ACS CENTRAL SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Robert D. Murphy, Ronnie V. Garcia, Seung J. Oh, Tanner J. Wood, Kyoo D. Jo, Javier Read de Alaniz, Ed Perkins, Craig J. Hawker
Summary: Describes the synthesis of functional hydrogels from 3-arm diblock copolypeptide stars, which achieve mechanical stability and biological activity through physical and photo-crosslinking, enabling direct ink writing of 3D objects with high precision and biological viability.
ADVANCED MATERIALS
(2023)
Article
Materials Science, Composites
Younghoon Kwon, Soyoung E. Seo, Jaejun Lee, Szabolcs Berezvai, Javier Read de Alaniz, Claus D. Eisenbach, Robert M. McMeeking, Craig J. Hawker, Megan T. Valentine
Summary: Additive manufacturing allows the creation of bio-inspired materials with complex architectures and diverse properties. By using a digital light processing strategy, polymer foams with controlled porosity were 3D printed by incorporating thermally expandable microspheres. The foams showed remarkable resilience under cyclic loading, maintaining their modulus and energy dissipation even at large deformations.
COMPOSITES COMMUNICATIONS
(2023)
Article
Polymer Science
Oscar Nordness, Joshua D. Moon, Nico Marioni, Everett S. Zofchak, Peter M. Richardson, Matthew R. Landsman, Lynn E. Katz, Craig J. Hawker, Venkat Ganesan, Rachel A. Segalman, Raphaele J. Clement
Summary: The effects of ligand basicity on water and ion transport within hydrogel membranes are investigated using a library of functionalizable poly(ethylene glycol) diacrylate (PEGDA) polymer networks. The study reveals that the self-diffusion of water molecules and ions is primarily driven by the hydration level of the membrane. The interaction between triflate anions and the polymer significantly reduces ion and water mobility.
Article
Polymer Science
KaitlinR. Albanese, Yoichi Okayama, Parker T. Morris, Matthias Gerst, Rohini Gupta, Joshua C. Speros, Craig J. Hawker, Chungryong Choi, Javier Read de Alaniz, Christopher M. Bates
Summary: We report a strategy to create degradable poly(acrylate) pressure-sensitive adhesives (PSAs) using 1,2-dithiolanes as drop-in replacements for traditional acrylate comonomers. The resulting PSA materials have comparable thermal and viscoelastic properties to nondegradable analogues, but can undergo reversible transformation between high and low molecular weights through oxidative repolymerization and reductive degradation. This simple and versatile chemistry could play a pivotal role in improving the sustainability of contemporary adhesives.
Article
Chemistry, Multidisciplinary
Robert D. Murphy, Colm Delaney, Srikanth Kolagatla, Larisa Florea, Craig J. Hawker, Andreas Heise
Summary: This study reports the design of photopolymerizable copolypeptides with tailored mechanical properties for additive manufacturing of 3D objects. The copolypeptides are able to form hydrogels suitable for direct ink writing or direct laser writing, leading to mechanically robust 3D structures.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Polymer Science
Yoichi Okayama, Taejun Eom, Michael Czuczola, Allison Abdilla, Jacob R. Blankenship, Kaitlin R. Albanese, Javier Read de Alaniz, Christopher M. Bates, Craig J. Hawker
Summary: The synthetic utility of heterotelechelic polydimethylsiloxane (PDMS) derivatives was enhanced by using a specifically designed silyl hydride (Si-H)-based initiator for anionic ring-opening polymerization (AROP) of hexamethylcyclotrisiloxane (D-3) monomers. The resulting PDMS polymers had high chain-end fidelity and heterotelechelic functionality. In situ termination of the propagating chain end with different chlorosilanes and functionalized alkenes further increased the diversity of the PDMS derivatives. The living nature of the polymerization allowed for the synthesis of narrow-dispersity polymers with a wide range of molar masses. Additionally, the feasibility of synthesizing supersoft bottlebrush networks using the PDMS macromonomers was demonstrated.
Article
Polymer Science
Gervase Ng, Zilong Wu, Tong Zhang, Anh Phong Dang, Yin Yao, Andrew R. J. Nelson, Stuart W. Prescott, Almar Postma, Graeme Moad, Craig J. Hawker, Cyrille Boyer
Summary: An oxygen-tolerant SI-PhotoRAFT technique has been developed for efficient synthesis of surface-tethered polymer brushes under low-energy near-infrared light. The technique takes advantage of the unique properties of NIR light to prepare polymeric coatings, even through barriers that are opaque to visible light. It enables precise modulation of brush height and sequential chain extension, as well as orthogonal control over polymerization and cross-linking processes using two different wavelengths.
Article
Chemistry, Multidisciplinary
Ronnie V. Garcia, Elizabeth A. Murphy, Nairiti J. Sinha, Yoichi Okayama, Juan Manuel Uruena, Matthew E. Helgeson, Christopher M. Bates, Craig J. Hawker, Robert D. Murphy, Javier Read de Alaniz
Summary: Shear-recoverable hydrogels with rapid self-recovery based on block copolypeptides have the potential to be used in extrudable and injectable 3D-printing applications. By synthesizing 3-arm star-shaped block copolypeptides with different side chains and block lengths, hydrogels with diverse microstructures and mechanical properties are prepared. The study reveals that non-canonical & beta;-sheet blocks based on phenyl glycine form more stable networks with superior mechanical properties and writability compared to natural amino acid counterparts.
Article
Polymer Science
Colton A. D'Ambra, Michael Czuczola, Patrick T. Getty, Elizabeth A. Murphy, Allison Abdilla, Souvagya Biswas, Jodi M. Mecca, Thomas D. Bekemeier, Steven Swier, Craig J. Hawker, Christopher M. Bates
Summary: A versatile synthetic platform is reported for the synthesis of high molecular weight graft copolymers with excellent control over molecular weight and grafting density. The controlled nature of side-chain growth is confirmed by selective degradation of the siloxane backbone, and grafting density and functionality can be further controlled by using a mixture of thiols.
JOURNAL OF POLYMER SCIENCE
(2023)
Article
Polymer Science
Kaitlin R. Albanese, Jacob R. Blankenship, Timothy Quah, Amy Zhang, Kris T. Delaney, Glenn H. Fredrickson, Christopher M. Bates, Craig J. Hawker
Summary: The potential of ABC triblock terpolymers in improving the mechanical properties of thermoplastic elastomers is demonstrated by comparing them with symmetric ABA/CBC analogs having similar molecular weights and volume fraction of B and A/C domains. The ABC architecture enhances elasticity through full chain bridging between discrete hard domains, minimizing mechanically unproductive loops. In addition, ABC triblock terpolymers allow for a higher fraction of hard-block domains while maintaining elasticity, which is traditionally only possible with non-linear architectures or highly asymmetric ABA triblock copolymers. These advantages provide a tunable platform to create materials with practical applications while improving our fundamental understanding of chain conformation and structure-property relationships in block copolymers.
Review
Nanoscience & Nanotechnology
Yiqing Wang, Zhenzhen Wu, Faezeh Makhlooghi Azad, Yutong Zhu, Lianzhou Wang, Craig J. Hawker, Andrew K. Whittaker, Maria Forsyth, Cheng Zhang
Summary: The incorporation of fluorine into battery components can improve the energy density, safety, and cycling stability of rechargeable batteries. This review explores the design and utilization of fluorine-containing species in advanced batteries, examining the relationship between their chemical structure and battery performance. It also discusses the challenges and opportunities of fluorinated batteries within the present regulatory framework.
NATURE REVIEWS MATERIALS
(2023)
