Article
Polymer Science
Xi Zhao, Guoxiang Wang, Yong Gao, Chong Cheng
Summary: This study demonstrated a robust method for the efficient preparation of mixed shell polymer nanoparticles (MSPNs) with various morphologies using polymerization-induced self-assembly (PISA) of Y-shaped ABC miktoarm star copolymers. PCL-TTC-PMMA copolymers containing a trithiocarbonate (TTC) group were synthesized and used as macromolecular chain transfer agents (CTAs) and stabilizers to mediate reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization. The factors influencing the morphologies of MSPNs during PISA were investigated, and their different PISA behaviors compared to linear PMMA-TTC were unraveled.
Article
Polymer Science
Ru Deng, Chengyuan Wang, Marcus Weck
Summary: We report a hydrogen-bonded supramolecular miktoarm star polymer containing three distinct helical arms. The assembly is driven by the hydrogen bonding between Hamilton Wedge (HW) and barbituric acid (Ba). This modular approach provides a strategy for preparing nonlinear supramolecular ensembles with topologically diverse building blocks.
Article
Chemistry, Physical
Min Liu, Jacob R. Blankenship, Adam E. Levi, Qiang Fu, Zachary M. Hudson, Christopher M. Bates
Summary: Polymers with controlled structure and function are highly sought after in various fields, including life sciences and nanotechnology. Miktoarm stars, a type of branched block copolymers with different arm compositions, have gained significant attention due to their distinct physical properties compared to linear block copolymers. This perspective article highlights the recent developments and historical context in the field of miktoarm star polymers, including design strategies, synthetic techniques, and advanced characterization tools. It serves as a resource for inspiring future research in this exciting class of materials at the intersection of chemistry, physics, and advanced technology.
CHEMISTRY OF MATERIALS
(2022)
Article
Polymer Science
Konstantinos Ntetsikas, Dimitrios Moschovas, George Zapsas, Ioannis Moutsios, Konstantina Tsitoni, Gkreti-Maria Manesi, Azat F. Nabiullin, Nikos Hadjichristidis, Dimitri A. Ivanov, Apostolos Avgeropoulos
Summary: This study focuses on the synthesis and characterization of linear and non-linear copolymers of PB-b-PI sequence and their miktoarm star copolymers, highlighting the high segment-segment interaction parameter between the polydiene blocks. The self-assembly properties of these copolymers are of major importance due to the nature of the blocks. The results suggest promising properties and consistent bulk morphology compared to other similar systems, especially in rheological studies.
Article
Polymer Science
Eman Ahmed, C. Tyler Womble, Jinwon Cho, Kristen Dancel-Manning, William J. Rice, Seung Soon Jang, Marcus Weck
Summary: Compartmetalized micelles are prepared through self-assembly of linear triblock terpolymers with control over block sequence and distribution, offering a facile approach for target material synthesis. Various morphologies such as core-shell-corona, disk-like, raspberry-like and worm-like are observed using cryogenic transmission electron microscopy and dissipative particle dynamics simulations.
Article
Polymer Science
Jie Xiao, Qun He, Minjun Yang, Haoquan Li, Xiandeng Qiu, Binghua Wang, Bin Zhang, Weifeng Bu
Summary: The hierarchical self-assembly behaviors of amphiphilic miktoarm star copolymers with pathway complexity were reported, leading to the formation of complex structures in solution.
Article
Polymer Science
Anna Mielanczyk, Maria Kupczak, Olesya Klymenko, Lukasz Mielanczyk, Sebastian Arabasz, Krystian Madej, Dorota Neugebauer
Summary: Well-defined miktoarm star-shaped polymers and linear block copolymers have been successfully synthesized based on a heterofunctional glucose derivative initiator, N,N'-dimethylaminoethyl methacrylate (DMAEMA), using a combination of atom transfer radical polymerization (ATRP) and ring-opening polymerization (ROP) techniques followed by click reactions. The presence of salts in polymer solutions affects the phase transformation and aggregate sizes, with the critical aggregation concentration (CAC) decreasing with decreasing DMAEMA unit content. TEM and AFM analysis reveal the microstructure changes in samples with different compositions of polyester arms.
Review
Polymer Science
Athanasios Skandalis, Theodore Sentoukas, Despoina Giaouzi, Martha Kafetzi, Stergios Pispas
Summary: RAFT polymerization is a versatile and precise technique for synthesizing linear ABC-type triblock terpolymers, which can self-assemble into different nanostructures based on their composition and external stimuli. Star-shaped polymers, on the other hand, exhibit a more stable nanostructure with distinct crosslinked core and arm blocks for smart applications.
Article
Chemistry, Multidisciplinary
Qilei Song, Hong Qiu, Lijun Liu, Guangzhao Zhang, Frederic Peruch, Stephane Carlotti, Junpeng Zhao
Summary: One-step sequence-selective block copolymerization requires strict catalytic control of monomer activity and enchainment order, especially for A(n)B(m)-type block copolymers from simple binary monomer mixtures. In this study, ethylene oxide (EO) and N-sulfonyl aziridine (Az) form a valid pair with a bicomponent metal-free catalyst. The optimal Lewis acid/base ratio allows the two monomers to block-copolymerize strictly in a reverse order (EO-first) compared to the conventional anionic route (Az-first). The livingness of the copolymerization enables the one-pot synthesis of multiblock copolymers by adding mixed monomers in batches. Calculation results suggest that the Janus effect of Lewis acid on the two monomers is crucial for enlarging the activity difference and reversing the enchainment order.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Polymer Science
Christos Pantazidis, Stelios Andreou, Georgia Nikolakakou, Emmanouil Glynos, Georgios Sakellariou
Summary: This study reports the synthesis and molecular characterization of a series of novel miktoarm star copolymers for single-ion electrolytes in lithium battery applications. The macromolecular architecture and the ratio of lithium ions to ethylene oxide units were found to have a significant impact on the properties of the materials.
Article
Multidisciplinary Sciences
Jiaxi Xu, Xin Wang, Nikos Hadjichristidis
Summary: The study demonstrates that the one-pot ring-opening terpolymerization using tert-butylimino-tris(dimethylamino)phosphorene as a catalyst can produce perfectly alternating diblock terpolymers with highly controllable molecular weights and narrow molecular weight distributions.
NATURE COMMUNICATIONS
(2021)
Article
Polymer Science
Yeseong Seo, Dokyung Woo, Luyang Li, Weihua Li, Jin Kon Kim
Summary: The phase behavior of polystyrene-(polystyrene-b-poly(2-vinylpyridine))(3) miktoarm star copolymer was investigated, with the volume fraction of the PS block (f(PS)) and the chain asymmetry of the PS chain (t) found to significantly influence the phase behavior. Different f(PS) and t values resulted in the formation of distinct structures, consistent with theoretical predictions.
Article
Polymer Science
Qingfu Ban, Yan Li, Yusheng Qin, Yaochen Zheng, Jie Kong
Summary: This study synthesized hyperbranched star poly(vinyl ether ester)s (mPEG-hb-PVEEs) amphiphiles with multimodal molecular weight distribution via one-pot Am+Bn+C1 step-growth polymerization, and deduced a convenient expression of the number ratio of monomeric structural units (NA/NB) based on topological analysis to describe the cyclic defect of intramolecular cyclization. The introduction of long-chain terminators and changes in the molar feed ratio significantly affected the NA/NB, leading to differences in the influence of number of macromolecules and intramolecular cyclization, which ultimately impacted the aqueous self-assembly behavior of mPEG-hb-PVEEs amphiphiles.
EUROPEAN POLYMER JOURNAL
(2021)
Article
Chemistry, Physical
Ivan D. Rodichkin, Rustam A. Gumerov, Igor I. Potemkin
Summary: Amphiphilic miktoarm star copolymers with one long solvophobic arm and several short solvophilic arms were studied in a selective solvent. Different morphologies were obtained, and the diagram of states was found to be different from the diagram of linear diblock copolymers. The increase of the number of solvophilic arms led to the transition from vesicles to cylinders, and then to spherical micelles. The increase of solvent selectivity shifted the stability region of cylindrical micelles to more symmetric compositions.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2022)
Article
Polymer Science
Chao Chen, Friederike Richter, Junliang Zhang, Carlos Guerrero-Sanchez, Anja Traeger, Ulrich S. Schubert, Anchao Feng, San H. Thang
Summary: This study reports the feasibility of synthesizing well-defined miktoarm star polymers containing peptide arms in an automated parallel synthesizer, providing a new method for accessing complex polymer structures for different applications.
EUROPEAN POLYMER JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Huan Qiu, Ting Shen, Zhening Yang, Feng Wu, Xiaohong Li, Yingfeng Tu, Jun Ling
Summary: Janus polymerization was utilized to synthesize multiblock copolymers with self-assembly capabilities, good shape memory properties, and potential applications in biomedical devices. The distinguishable chemical structures and thermal properties between Janus MBCPs and cationic random copolymers were confirmed, providing insights into the unique features of Janus polymerization for advanced material design and applications.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Polymer Science
Jiawen Song, Kaihao Chen, Yuanhao Feng, Xufeng Ni, Jun Ling
Summary: This study presents a novel one-pot orthogonal strategy for the utilization of disubstituted delta-valerolactone in the synthesis of a series of amphiphilic polymers, which hold significant implications for the transformation of carbon dioxide.
JOURNAL OF POLYMER SCIENCE
(2022)
Article
Polymer Science
Yan-Zhi Lu, An-Qi Gu, Tian-Lun Shen, Ji-Hong Sun, Jun Ling
Summary: Modifications at polypeptide side chains have been found to affect conformation and properties. The synthesis of poly(S-allylcysteine) (PAC) with unsaturated bonds and thioether moieties provides active binding sites and enzymatic catalytic sites. These polypeptides may find applications in drug delivery, biosensing, and nanoreactor.
CHINESE JOURNAL OF POLYMER SCIENCE
(2022)
Article
Engineering, Biomedical
Yuwen Lu, Tanchen Ren, Hua Zhang, Qiao Jin, Liyin Shen, Mengqi Shan, Xinzhe Zhao, Qichao Chen, Haoli Dai, Lin Yao, Jieqi Xie, Di Ye, Tengxiang Lin, Xiaoqian Hong, Kaicheng Deng, Ting Shen, Jiazhen Pan, Mengyan Jia, Jun Ling, Peng Li, Yue Zhang, Huanan Wang, Lenan Zhuang, Changyou Gao, Jifu Mao, Yang Zhu
Summary: This study fabricated stiff polymeric microneedles with backward-facing barbs inspired by honeybee stingers and embedded them into elastomer films to produce self-interlocking microneedle patches. The barbing pattern was adjusted to increase interlocking efficiency. The microneedle patches demonstrated strong tissue adhesion and were successfully implanted onto beating hearts. They reduced cardiac wall stress and maintained left ventricular function. The microneedle patches were minimally invasive and did not require sutures or adhesives.
ACTA BIOMATERIALIA
(2022)
Article
Chemistry, Multidisciplinary
Kaihao Chen, Zhiqi Zhu, Tianwen Bai, Yixuan Mei, Tianlun Shen, Jun Ling, Xufeng Ni
Summary: We designed and performed a novel strategy to produce polyesters using CO2 and olefins, by individually synthesizing PCL and EVL oligomers through anionic ring-opening polymerization and conjugated addition oligomerization, and then inserting EVL oligomers into PCL by transesterification, resulting in polyesters with tunable topology and composition.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Engineering, Biomedical
Jingya Xia, Liying Wang, Tianlun Shen, Ping Li, Peiyun Zhu, Shengnan Xie, Zhenyan Chen, Fei Zhou, Jingfeng Zhang, Jun Ling, Xiangrui Liu, Hong Yu, Jihong Sun
Summary: Despite the initial promise of photothermal ablation (PTA) therapy, the inability to completely ablate large tumors is problematic. This study developed a smart photothermal nanosystem (PBM) based on FDA-approved Prussian blue (PB) nanoparticles, doped with Mn (III) to address this issue. The PBM nanosystem amplified the PTA-induced cGAS-STING pathway, leading to a robust immune response and suppression of both local residual and distant tumors.
ACTA BIOMATERIALIA
(2023)
Article
Chemistry, Multidisciplinary
Yixuan Mei, Kaihao Chen, Jiayu Gu, Jun Ling, Xufeng Ni
Summary: This study reports the successful synthesis of a copolymer of 2-methyltetrahydrofuran (2-MeTHF) and beta-butyrolactone (BBL) through Sc(OTf)(3)-catalysed cationic ring-opening copolymerization. The possibility of copolymerization was verified by density functional theory (DFT) calculations. The obtained copolymer, poly(2-MeTHF-co-BBL), showed promising properties and potential as an environmentally friendly material.
Article
Nanoscience & Nanotechnology
Kai Hao, Ronglu Cui, Lifeng Fang, Jun Ling, Baoku Zhu
Summary: In this study, a neutral surface of polysarcosine (PSar), a hydrophilic polypeptoid, was successfully synthesized and modified to enhance its compatibility with water, reduce protein adsorption and cytotoxicity, and demonstrate good hemocompatibility and antifouling properties.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Polymer Science
Siqi Wang, Tianlun Shen, Kai Hao, Xinfeng Tao, Jihong Sun, Jun Ling
Summary: Hyperbranched poly(a-amino acid)s have attracted attention for their biocompatibility, degradability, and bioactivity. Unique polymerization reactions of di-NNPC resulted in hyperbranched polypeptoids instead of gels. The molecular weights of the hyperbranched polypeptoids were controlled by tuning the initial concentrations of monomer and basic catalyst. The residual glycine pendant groups on the polymer chains were used for Gd3+ complexation and post-modification, making the hyperbranched polypeptoids multifunctional single molecular micelles applicable as contrast agents and probes in magnetic resonance imaging and photoluminescence.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2023)
Review
Polymer Science
Ting Shen, Kaihao Chen, Yougen Chen, Jun Ling
Summary: To address the plastic waste crisis, there are efforts to develop sustainable polymer materials that can degrade through disposing and decomposing to small molecules (DDM) or via chemical recycling to monomers (CRM). Polyacetals, a type of pH-responsive polymers, can degrade under acidic conditions but remain stable under neutral and basic conditions. Their synthesis through cationic ring-opening polymerization (CROP) has challenges but recent advancements in CRM have renewed interest in this method. Polyacetals offer recyclable materials with DDM and CRM potential, expanding closed-loop recycling options and improving degradation properties of traditional polyesters and polyolefins.
MACROMOLECULAR RAPID COMMUNICATIONS
(2023)
Article
Multidisciplinary Sciences
Jie Zhang, Tianwen Bai, Weixi Liu, Mingzhao Li, Qiguang Zang, Canbin Ye, Jing Zhi Sun, Yaocheng Shi, Jun Ling, Anjun Qin, Ben Zhong Tang
Summary: High refractive index polymers (HRIPs) with excellent optical transparency are prepared by using organobase catalyzed polymerization. The HRIPs exhibit high refractive indices, high molecular weights, and low propagation loss. The polymers also have aggregation-induced emission feature for monitoring the uniformity and continuity of optical waveguides.
NATURE COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Kaihao Chen, Yixuan Mei, Zhuorui Zhang, Jun Ling, Xufeng Ni
Summary: As a substituted-delta-valerolactone, alpha-ethylidene-delta-vinyl-delta-valerolactone (EVL) offers a method to utilize carbon dioxide and 1,3-butadiene in producing functional polymers. Recent successful attempts in polymerizing EVL have led to the development of novel synthetic strategies and functional polymers. This review highlights the ring-opening reactions of EVL and its derivatives, as well as the ring-opening (co)polymerizations, showcasing the unique properties of the obtained functional polymers and their application potential in various fields.
Article
Polymer Science
Jianping Wang, Peng Zhou, Ting Shen, Songyi Xu, Tianwen Bai, Jun Ling
Summary: This study developed a novel method to synthesize glycine-rich poly-(amino acid)-s (PAAs) through controlled ring-opening copolymerization. The synthesized copolymers exhibited predictable molecular weights and tunable glycine incorporation, and could form nanoparticles or hydrogel in water. The beta-sheet folding of poly-(Gly-r-Lys) remained intact in a neutral environment. This strategy opens up new possibilities for engineering glycine-rich PAAs and expanding their applications.
Article
Materials Science, Biomaterials
Shangyu Chen, Peng Zhou, Wan Yang, Danni Hu, Pengfei Chen, Pengfei Sun, Jun Ling, Quli Fan
Summary: In this study, a modified near-infrared II (NIR-II) small-molecule-based polymer was prepared for efficient breast cancer pulmonary metastasis imaging. The polymer showed good solubility, high fluorescence quantum yield, and prolonged blood circulation half-life, and demonstrated better tumor accumulation capability even at low dye concentration. The successful use of this polymer in noninvasive NIR-II fluorescence imaging for breast cancer pulmonary metastasis was demonstrated.
BIOMATERIALS SCIENCE
(2023)
Article
Nanoscience & Nanotechnology
Huiyang Wang, Siqi Wang, Xisong Zhu, Wenxiu Ding, Tianlun Shen, Hongjie Fan, Yanhua Zhang, Lijun Peng, Hong Yuan, Xiangrui Liu, Jun Ling, Jihong Sun
Summary: In this study, an iron-based solid lipid nanoparticle (SLN) was developed, which can be absorbed by the intestinal wall and enhance contrast in MRI. Experimental results using mouse models showed that the SLN has better diagnostic value for acute ulcerative colitis and colon adenocarcinoma. Confocal fluorescence microscopy confirmed that the SLN mainly distributes in the intestinal mucosa and tumor capsule.
INTERNATIONAL JOURNAL OF NANOMEDICINE
(2022)
