Article
Chemistry, Applied
Aoi Nakashima, Kaho Kohori, Kazuya Yamamoto, Jun-ichi Kadokawa
Summary: Chitin hexanoate-graft-poly(epsilon-caprolactone) (ChHex-g-PCL) was found to be thermoplastic, and the thermoplasticity was confirmed by the formation of a melt-pressed film. Chitin hexanoates were prepared by hexanoylation of chitin and then the surface-initiated ring-opening graft polymerization of epsilon-caprolactone was conducted to graft PCL chains onto the hydroxy groups of chitin hexanoates. The molar substitution and degree of polymerization of the PCL graft chains were influenced by the catalyst, reaction time, and degree of substitution.
CARBOHYDRATE POLYMERS
(2022)
Article
Polymer Science
Yalei Liu, Xinhui Kou, Chen Xu, Wei Zhou, Hongshu Zhang, Fusheng Liu, Yong Shen, Zhibo Li
Summary: The chemoselective ring-opening copolymerization (ROCP) of MVL with CL has been achieved using an organophosphazene/urea binary catalyst, resulting in functional P(MVL-co-CL) copolyesters with a modifiable double bond. The pendent double bond of the copolyesters can be post-functionalized by the thiol-Michael addition reaction to obtain thiolated copolyesters.
Article
Polymer Science
Victoria J. Barber, Meredith A. Borden, Jill W. Alty, Ly D. Tran, Hilmar Koerner, Luke A. Baldwin, Erik J. Alexanian, Frank A. Leibfarth
Summary: There is an increasing demand for degradable polymers in sustainable plastics and medical implants. To improve their usability, it is necessary to have a better understanding of degradation factors and develop new tools for modulation. In this study, poly(caprolactone) was modified through C-H xanthylation, resulting in changes in material properties and slower degradation. The interplay between molecular and materials characteristics was found to impact the degradation rate.
Article
Biochemistry & Molecular Biology
Ahmed Abd El-Fattah, Elizabeth Grillo Fernandes, Federica Chiellini, Emo Chiellini
Summary: Amphiphilic copolymers with interesting architecture and tunable properties are promising materials for biomedical applications. Enzymatic catalysis provides a suitable alternative for the preparation of these materials without the use of toxic catalysts. The structure-property relationship of copolymers was studied by varying the molecular weight of Pluronic (EPE) and the molar ratios between ε-caprolactone monomer and EPE macro-initiator (M/In). The obtained copolymers were chemically characterized and their morphologies evaluated. The results showed a correlation between the differential scanning calorimetry data and X-ray diffraction data, suggesting the importance of the central block length in crystal formation. Preliminary cytotoxicity experiments confirmed the non-toxic nature of the copolymers.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Polymer Science
Chun-Juei Chang, Wei Lee, Yu-Chi Liou, Yu-Lun Chang, Yi-Chun Lai, Shangwu Ding, Hsuan-Ying Chen, Hsing-Yin Chen, Yung-Chi Chang
Summary: The study demonstrated that dinuclear aluminum complexes exhibited higher catalytic activity than mononuclear aluminum complexes, particularly those with 1,3-substituted phenyl ligands. One Al atom in the dinuclear Al system acted as an electron-withdrawing group, influencing the other Al atom through associated aromatic ligands, thereby enhancing catalytic activity for the ROP of CL.
EUROPEAN POLYMER JOURNAL
(2022)
Article
Materials Science, Composites
Reyhan Ozdogan Tasci, Mehmet Arslan, Mehmet Atilla Tasdelen
Summary: Utilizing click chemistry for the fabrication of polymeric nanocomposites shows great promise in improving the structure-property relationship of materials. This study successfully prepared poly(epsilon-caprolactone)/clay nanocomposites via Diels-Alder click reaction, demonstrating excellent performance.
POLYMER COMPOSITES
(2022)
Article
Polymer Science
Oleksandr Ivanchenko, Stephane Mazieres, Rinaldo Poli, Simon Harrisson, Mathias Destarac
Summary: In this study, the ring-opening copolymerisation of different-sized thionolactones with vinyl pivalate was mechanistically investigated. The results demonstrated the crucial effect of ring size on the copolymerisation and ring-opening ability of thionolactone, and the importance of stabilizing the intermediate ring-retained radical for thionolactone reactivity was confirmed through experimental and computational methods.
Article
Polymer Science
Yutthana Wongnongwa, Setsiri Haesuwannakij, Kwanchanok Udomsasporn, Phongnarin Chumsaeng, Anucha Watcharapasorn, Khamphee Phomphrai, Siriporn Jungsuttiwong
Summary: Polymerization of biodegradable lactide and lactone has been extensively investigated. Density functional theory calculations were used to study the initiation and first propagation for ring-opening polymerization mechanisms of L-lactide (LA) and e-caprolactone (CL) on aluminum complexes. The results showed that the ROP mechanisms of LA and CL on different catalysts were classified into homopolymerization and copolymerization. The understanding gained in this study could contribute to the development of high-performance catalysts for biodegradable lactide and lactone ROP reactions.
Article
Polymer Science
Watcharee Funfuenha, Winita Punyodom, Puttinan Meepowpan, Wanich Limwanich
Summary: Microwave irradiation was successfully used to improve the solvent-free ring-opening polymerization of ε-caprolactone with different n-butyltin(IV) chloride initiators. The performance of these initiators was compared to the conventional tin(II) 2-ethylhexanoate. The presence of chlorine atom in the n-butyltin(IV) chloride initiators played a significant role in controlling the molecular weight of the polymer.
Article
Polymer Science
Monique J. Leite, Tamara Agner, Fabricio Machado, Brenno A. D. Neto, Pedro H. H. Araujo, Claudia Sayer
Summary: This study utilized an iron-containing imidazolium-based ionic liquid as a catalyst to efficiently catalyze the ring-opening polymerization of epsilon-caprolactone under mild reaction conditions, resulting in the synthesis of polycaprolactones with high yields and narrow molecular weight distributions.
JOURNAL OF POLYMER RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Eloy Rodriguez-deLeon, Moustapha Bah, Jose E. Baez, Maria T. Hernandez-Sierra, Karla J. Moreno, Alejandro Nunez-Vilchis, Jose Bonilla-Cruz, Kenneth J. Shea
Summary: In this study, three xanthophylls were used for the first time as initiators in the synthesis of sustainable xanthophyll-containing poly(epsilon-caprolactone). The obtained polyesters were characterized and evaluated for their use as additives in green lubricants. The results showed that xanthophylls-PCL exhibited better tribological behavior than current additives, indicating their potential as future commercial materials.
Article
Materials Science, Composites
Hossein Ebrahimi, Farhad Sharif, Ahmad Ramazani SA
Summary: The synthesis of nanocomposites through in situ grafting polymerization in the presence of modified titanium dioxide nanoparticles has successfully produced copolymers with different structures, among which the nanocomposite with a LLA/CL mass ratio of 70/30 exhibits the best mechanical properties.
POLYMER COMPOSITES
(2021)
Article
Polymer Science
Supriya Atta, Jarrod Cohen, Joachim Kohn, Adam J. Gormley
Summary: Ring opening polymerization (ROP) is typically conducted using anhydrous reagents and inert atmosphere, which are barriers for non-experts. Here, two new techniques for limited ROP of epsilon-caprolactone (CL) without pre-drying reagents were developed using a laboratory oven. By evaporating water in a vacuum oven or polymerizing through water with titanium isopropoxide (TTIP), variable chain lengths and molecular weight distributions of PCL were achieved, with TTIP showing better performance for higher molecular weights and block copolymer formation.
Article
Polymer Science
Charalampos Pronoitis, Minna Hakkarainen, Karin Odelius
Summary: By rational design of the microstructure of PHUs and utilizing solubility as an enabling tool, complex architectures can be realized with benign reagents and atom-economical reactions, without harsh reaction conditions and solvents. This approach expands the synthetic intricacy for PHUs and could potentially broaden their applications and opportunities in the future.
Article
Chemistry, Inorganic & Nuclear
Boying Yu, Xiaocheng Xu, Zhen-Na Huang, Keyan Tao, Hao-Ling Sun, Qing-Zheng Yang, Wenguang Wang
Summary: We present a high-spin iron system supported by dipyrromethene ligands for the ring-opening polymerization of epsilon-caprolactone. The iron(II) complex, (dipyrrin)2Fe, with an S = 2 electronic configuration, reacts easily with 2,4,6-tri-tert-butylphenoxyl radical to form a high-spin S = 5/2 iron(III) aryloxide complex. At low loading, this ferric aryloxide efficiently performs CL polymerization, producing high molecular weight and narrow polydispersity PCLs.
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)