Marine Drugs
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2017
·Vol. 15
·期 7
·223
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IF 3.503
Na Li,Huanhuan Wang,Xiaosai Qu,Yu Chen
ROMP is an effective method for preparing functional polymers due to its having characteristics of “living” polymerization and rapid development of catalysts. In the present work, poly(norbornene-methylamine), a mimic of chitosan, was synthesized via ROMP reaction. The amino-protected product, 5-norbornene-2-(N-methyl)-phthalimide, was prepared by a reaction of 5-norbornene-2-methylamine with phthalic anhydride, which was then subjected to the ROMP reaction in the presence of Hoveyda-Grubbs 2nd catalyst to afford poly(norbornene-(N-methyl)-phthalimide). The target product, poly(norbornene-methylamine), was obtained by deprotection reaction of poly(norbornene-(N-methyl)-phthalimide). The products in each step were characterized by FTIR and1H-NMR, and their thermal stabilities were determined by TG analysis. The effects of molar ratio between monomer ([M]/[I]) and catalyst on the average relative molecular weight (Mn¯) and molecular weight distribution of the produced polymer products were determined by gel permeation chromatography (GPC). It was found that theMn¯of poly(norbornene-(N-methyl)-phthalimide) was controllable and exhibited a narrow polydispersity index (PDI) (~1.10). The synthesis condition of 5-norbornene-2-(N-methyl)-phthalimide was optimized by determining the yields at different reaction temperatures and reaction times. The highest yield was obtained at a reaction temperature of 130 °C and a reaction time of 20 min. Our work provides a new strategy to synthesize polymers with controllable structures and free –NH2groups via ROMP.Keywords:ROMP;poly(norbornene-methylamine);controllable;living polymerization;chitosan
研究领域:
高分子化学
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生物材料科学
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PubMed
高影响因子
CHEMICAL RESEARCH IN CHINESE UNIVERSITIES
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2018
·Vol. 34
·期 5
·828-832
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IF 1.248
Qiao Yaping,Yuan Xiaoyan,Zhao Yunhui,Ren Lixia
Controlled preparation of brush polymers is important in the design of functional materials. In this study, poly( tert -butyl acrylate) macromonomers functionalized with norbornenyl end group(NB-P t BA) were synthesized via atom transfer radical polymerization in three different molecular weights, 2000(NB-P t BA-2k), 3000(NB-P t BA-3k), and 8000(NB-P t BA-8k). Additionally, brush polymers with P t BA as side chains were synthesized via ring-opening metathesis polymerization(ROMP). Kinetic studies on ROMP of NB-P t BA showed that there was a ceiling degree of polymerization(CDP) for the brush polymers, beyond which the polymerization of NB-P t BA was out of control. For brush polymers of P[NB-P t BA-2k] and P[NB-P t BA-3k], CDPs were estimated to be ca . 400, but the value of P[NB-P t BA-8k] was ca . 100. Therefore, the controlled ROMP of brush polymers was critical at the CDP limit with increased macromonomer molecular weight.
研究领域:
材料科学
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高分子化学
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高影响因子
Polymer Chemistry
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2021
·Vol. 12
·期 46
·6745-6754
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IF 5.582
Zhi-Hao Zhang,Shan-Qing Peng,Shumeng Chi,Hanyuan Chen,Lei Fan,Yan Liu,Xiaohua Ma,Mu-Hua Huang
Porous organic polymers (POPs) are a class of promising materials for overcoming environmental and energy issues worldwide. However, their amorphous nature makes structural characterization in the solid state very challenging. In addition, developing facile synthesis methods and applications for POPs with novel structures remain urgent issues requiring improvement. In this work, novel porous organic polymers (named BIT-POPs) with isolated trans-alkene linkages were synthesized via cross-linking bis-norbornene via ring opening metathesis polymerization (ROMP) in an extremely mild and fast manner. Spectral editing approaches, such as 13C-CPMAS, 13C-CPPI, and 13C-CPNQS, relating to solid-state NMR were used to distinguish the overlapping NMR signals of insoluble BIT-POPs, and two-dimensional 1H–13C HETCOR spectra were used. Also, BIT-POP-5 was added to a polysulfone matrix as a porous filler to form a mixed-matrix membrane, which showed a 126% increase in CO2 permeability during gas separation.
研究领域:
材料科学
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环境科学
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能源科学
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高影响因子
MICROCHEMICAL JOURNAL
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2025
·
IF 5.1
Shijin Zhou,Nan Ma,Kefeng Ma,Jinming Kong,Xueji Zhang,Huaixia Yang
Ultrasensitive quantitative detection of Staphylococcus aureus ( S. aureus ) is critically important for preventing food-borne illnesses caused by this pathogen. In this study, an electrochemical biosensor for accurate detection of S. aureus was developed for the first time by in situ ring-opening metathesis polymerization (ROMP) of bacterial surface proteins. In brief, the glassy carbon electrode (GCE) was functionalized via electrochemical reduction of aryl diazonium salts to provide binding sites for specific capture probe-aptamer. 2,2,6,6-tetramethylpiperidin-4-ylamine (TEMPO) was modified on the ROMP polymer by post-functionalization method to achieve signal amplification. In the concentration range of 1.0 × 10 1 CFU/mL ∼ 1.0 × 10 8 CFU/mL, the detection limit of the electrochemical biosensor for S. aureus was 2.2 CFU/mL. In addition, the sensor has excellent reproducibility and recognition ability, and can accurately detect S. aureus in the presence of a variety of bacteria. To validate practical utility, the biosensor was successfully applied to detect S. aureus in real food samples—including milk and orange juice—yielding high recovery rates and reliable quantification. The sensor adopts a mild and environmentally friendly ROMP signal amplification strategy and has excellent analytical performance, which has important potential in the field of accurate identification of food-borne pathogens.
研究领域:
分析化学
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生物传感器
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高分子化学
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电化学
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食品安全
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病原体检测
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DOI
高影响因子
LANGMUIR
·
2023
·
IF 3.9
Xinting Wu,Ning Ren,Gangsheng Tong,Xinyuan Zhu
Ring-opening metathesis polymerization (ROMP) is a powerful method to graft various types of polymer chains to a given surface. While surface-initiated ROMP (SI-ROMP) serves as an efficient tool for surface modification and is therefore widely reported, the method requires grafting (1) the olefin substrate and (2) the metathesis catalyst to the surface prior to the polymerization with multiple synthetic and work up steps. To overcome this difficulty, we proposed the use of the chain-transfer reaction as an alternative method for surface modification. Terminal olefins are grafted to the surface without the need to graft the metathesis catalysts, and polymers with olefin backbones are polymerized and grafted simultaneously via both ROMP and chain transfer (cross-metathesis between olefins from backbones and surfaces). Compared to SI-ROMP, this surface-chain transfer ROMP (SC-ROMP) method avoids grafting the catalyst and growing polymer chains from the surface and could be achieved in a single step. Various types of surfaces like carbon nanotubes, carbon fibers, graphene nanosheets, and silica microspheres are used for demonstration. We envision that this work could bring a convenient and effective solution to surface modification via ROMP.
研究领域:
材料科学
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化学工程
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DOI
PubMed
高影响因子
ANALYTICA CHIMICA ACTA
·
2026
·
IF 6.1
Dan Qin,Shijin Zhou,Davaasuren Tsendjav,Jing Li,Jinming Kong
Background The early and accurate detection of miRNA-21 is of great significance for both lung cancer diagnosis and livestock health monitoring, given its conserved sequence across mammals. Herein, we report an enzyme-free electrochemical biosensor based on surface-initiated ring-opening metathesis polymerization (ROMP) for the ultrasensitive detection of miRNA-21. A thiolated peptide nucleic acid (PNA) probe was immobilized on a gold electrode to capture the target. The formed PNA–RNA hybrid duplex provided a high-density phosphate backbone that served as a coordination anchor for Zr(IV) ions, enabling directional immobilization of acrylic acid monomers via Zr–O–P/Zr–O–C bridges. Subsequent addition of a water-soluble ruthenium catalyst (AquaMet) initiated in situ ROMP of cyclopentenyl ferrocene (CFc) monomers, converting a single hybridization event into long polymer chains densely decorated with electroactive ferrocene units for substantial signal amplification. Results Under optimized conditions, the biosensor exhibited a wide linear range from 0.1 fM to 0.1 nM, with an ultralow detection limit of 67 aM. It showed excellent selectivity against single-base mismatches, as well as good reproducibility and storage stability. Importantly, the sensor maintained satisfactory recovery rates in diluted human serum and demonstrated strong anti-interference capability in complex matrices. Significance Owing to the sequence conservation of miRNA-21 across mammals and the mild, enzyme-free nature of the ROMP strategy, this platform holds great potential for both clinical lung cancer screening and on-site health monitoring in livestock and poultry.
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高影响因子
MICROCHEMICAL JOURNAL
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2026
·
IF 5.2
Shijin Zhou,Zhidan Tian,Qinyuan Xu,Jinming Kong,Xueji Zhang
Orthogonal dual-stage ROMP cascade enables ultrasensitive miRNA-21 detection. • Scaffold construction and signal amplification are decoupled. • The sensor detects miRNA-21 with a detection limit of 2.24 aM. • High selectivity and reliable performance in complex serum matrices. Traditional ring-opening metathesis polymerization (ROMP)-based biosensors typically couple scaffold construction and signal amplification within a single polymerization step, which limits the independent optimization of mechanical stability and electrochemical performance. This study developed an orthogonal two-stage ROMP cascade amplification strategy that successfully decoupled these two processes. Target-specific hybridization first triggers Zr 4+ coordination, initiating surface-mediated metal-catalyzed ROMP to construct a dense polynorbornene scaffold bearing cyclic anhydride side chains. Subsequently, metal-free ROMP driven by visible light grafts high-density ferrocene monomers onto the pre-assembled scaffold, forming electroactive bottlebrush polymers. This biosensor achieves a detection limit for miRNA-21 as low as 2.24 aM, with a linear range from 10 aM to 1 nM, and exhibits excellent selectivity against mismatched RNA sequences, as well as reliable detection performance in complex serum matrices. The orthogonal cascade strategy proposed in this study provides a modular and versatile new platform for the ultrasensitive detection of low-abundance biomarkers. Download: Download high-res image (116KB) Download: Download full-size image
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高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2016
·
IF 3.205
Yubin Zhao,Lei Feng,Jinjin Gao,Yang Zhao,Shubo Wang,Vijay Ramani,Zhenlin Zhang,Xiaofeng Xie
A novel monomer who combined cross linker and functional groups together called 2,2'-(hexane-1,6-diyl)bis(2-methyl-2,3,3a,4,7,7a-hexahydro-1H-4,7-methanoisoindol-2-ium) iodide (HDHM-iodide) was synthesized and polymerized by Ring-opening Metathesis Polymerization (ROMP) to give a series of anion exchange membranes . The resulting monomers and polymers were characterized by 1 H and 13 C NMR, TGA . Directly cast from the polymerization solution on flat glass to form the clear, flexible anion exchange membrane. Swelling ratio and water uptake are only 6.2% and 28.04% at 60 °C for membrane with 2.32 mmol·g −1 ion exchange capacity (IEC). The conductivity of Poly (HDHM-Norbornene-hydroxide-12) and Poly(HDHM-Norbornene-chlorine-12) AEMs at room temperature up to 27 mS·cm −1 and 14 mS·cm −1 separately, and increased with temperature quickly. After 16 days immersed in 2 M NaOH solution, conductivity and IEC dropped at 60 °C in alkaline solution, 50% and 35% separately. The energy barrier of degradation pathways calculation reveled that Hofmann Elimination case 2 degradation pathway with the lowest energy barrier 12.181 kcal·mol −1 is most likely occurred when faced with hydroxide. Also, the energy barrier of Hofmann Elimination is lower than Nucleophilic Substitution degradation mechanism .
研究领域:
材料科学
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化学工程
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高影响因子
POLYMERS FOR ADVANCED TECHNOLOGIES
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2020
·Vol. 31
·期 11
·2492-2503
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IF 2.578
Fuqiang Zhou,Lucheng Qi,Xuelian He
A series of different molecular weight Polycyclooctene(PCOE) rubber were synthesized via ROMP with G 2 catalyst and Iso-polypropylene (iPP), PCOE and high density polyethylene (HDPE) blends were prepared by micro twin-screw extruder. The effects of PCOE molecular weight and content were investigated by studying the thermal, rheological and mechanical properties of the blends. We observed that the low molecular weight PCOE promoted the dispersion of HDPE, and as the molecular weight and content of PCOE rising, PCOE encapsulated HDPE particles entirely to form a connected core-shell network structure in PP matrix and a certain degree of micro-crosslinked structure which connected the PCOE ‘shell’. Micrographs of the fracture surfaces support the finding that PCOE promoted a finer dispersion and improved the morphological stability of the ternary blends as a compatibillizer. The increasing molecular weight of PCOE enhanced the molecular chains entanglement of the blends resulting in an increase on blends viscosity. The interfacial adhesion of PP/PCOE/HDPE ternary blends improved significantly as PCOE molecular weight increased from 12 kg/mol to 270 kg/mol. The impact strength of the PP/PCOE/HDPE blends increased by 3 times as compared with PP/HDPE blends owing to the addition of 15 wt% HDPE and 15 wt% PCOE( M n = 270 kg/mol).
研究领域:
材料科学
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高分子化学
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DOI
高影响因子
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
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2015
·Vol. 54
·期 10
·1396-1408
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IF 3.113
Xiaojuan Zhang,Qian Zhang,Chao Xie,Aiting Gao,Zheng Chang,Jung Kwon Oh,Peng Yang,Pengfei Li
Phosphonated and epoxy-containing norbornene based monomers were prepared by Diels–Alder reaction. They were then combined with three other commercial cyclic unsaturated monomers to synthesize phosphonated homopolymers and copolymers via ring opening metathesis polymerization (ROMP) using second-generation Grubbs catalyst. Glass transitions of these polymers were tunable in a broad range from −14 to 91 °C by varying the flexibility of comonomer. Interestingly, copolymerization with cyclopentene inhibited the crystallization of polycyclopentene, and instead, led to a copolymer with two T g s. Paradoxically, results from thermogravimetric analysis (TGA) were not consistent with the followed flame-retarding experiment, implying that the early weight loss from phosphonated moieties did not deleteriously affect the flame-resistant property which actually depended more on the percentage of char residual after thermal degradation. In application studies, the norbornene derivative phosphonated polymer was tested for the first time as flame retarding material, and showed significant self-extinguishing ability. In a second study, photolithography was also successfully performed via thiol-ene “click” chemistry, which allowed the phosphonated polymer a promising negative photoresist. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54 , 1396-1408
研究领域:
高分子化学
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材料科学
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DOI
高影响因子
Polymer Chemistry
·
2017
·Vol. 8
·期 44
·6709-6719
·
IF 5.375
Fei Fan,Chao Cai,Lei Gao,Jun Li,Ping Zhang,Guoyun Li,Chunxia Li,Guangli Yu
The protecting-group-free synthesis of versatile glycopolymers accelerated by microwave irradiation in an emulsion system is presented herein. Copper-catalyzed azide–alkyne cycloaddition (CuAAC) was employed to prepare a wide range of glycosylated hydrophilic monomers, and a series of glycopolymers were fabricated via ring-opening metathesis polymerization (ROMP). Our data revealed that phase transfer catalysis (PTC) in an emulsion system was more superior to that of homogeneous solvents (organic and aqueous solvents). Grubbs 2nd, Grubbs 3rd, and Hoveyda–Grubbs 2nd (H–G 2nd) catalysts were systematically screened from room temperature to 75 °C, of which the H–G 2nd catalyst exhibited more compatibility with microwave irradiation in emulsion polymerization. The efficiency of polymerization was significantly enhanced under microwave irradiation that was completed in less than 5 min for homopolymerization and within 15 min for multi-block polymerization. Six glycopolymers were successfully synthesized under optimum conditions. In addition, the surface plasmon resonance (SPR) analysis indicated that the mannose-functionalized multi-block glycopolymers (p-Glu-b-Man and p-Glu-b-Man-b-Fuc) exhibited dramatic improvements in their binding affinities to concanavalin A (ConA) as compared to the homoglycopolymer (p-Man). The robust approach developed in this study offers the efficient fabrication of versatile glycopolymers for potential biological and medical applications.
研究领域:
有机化学
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生物化学
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材料科学
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高影响因子
CHINESE JOURNAL OF POLYMER SCIENCE
·
2021
·Vol. 39
·期 8
·994-1003
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IF 3.603
Zhang Wan-Bin,Luo Jie,Wang Yan-Meng,Zhu Xiu-Zhong,Zhang Ce,Liu Jing,Ni Mei-Le,Zhang Guang-Hua
A series of hydroxyl-terminated polyethylenes (HTPE) bearing various functional side groups ( e.g. carboxyl, ester and butane groups) were synthesized by the combination of ring-opening metathesis polymerization (ROMP) and visible light photocatalytic thiol-ene reaction. The products are named as α, ω -dihydroxyl-poly[(propionyloxythio)methinetrimethylene] (HTPE carboxyl ), α, ω -dihydroxyl-poly[(methylpropionatethio) methinetrimethylene] (HTPE ester ) and α, ω -dihydroxyl-poly[(butylthio) methinetrimethylene] (HTPE butane ), respectively. The investigation of ROMP indicated that the molecular weight of resultant hydroxyl-terminated polybutadiene (HTPB) can be tailored by varying the feed ratios of monomer to chain transfer agent (CTA). The exploration of the photocatalytic thiol-ene reaction between HTPB precursor and methyl 3-mercaptopropionate revealed that blue light as well as oxygen accelerated the reaction. 1 H-NMR and 13 C-NMR results verified all the double bonds in HTPB can be modified, and the main chain of resultant polymer can be considered as polyethylene. Subsequently, relationship between the structure of side groups and the thermal properties of functional PEs was studied. And the results suggested that the T g was in the order of HTPE butane
研究领域:
高分子化学
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材料科学
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高影响因子
危险品化学品经营许可证（带存储）