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JOURNAL OF BIOMATERIALS APPLICATIONS · 2016 · IF 1.988

Impact of hydrogenation on physicochemical and biomedical properties of pH-sensitive PMAA-b-HTPB-b-PMAA triblock copolymer drug carriers

Feng Xu,Jing-Wen Xu,Yan-Ling Luo

pH-Sensitive poly(methacrylic acid)-block-hydroxyl-terminated polybutadiene-block-poly(methacrylic acid) (PMAA-b-HTPB-b-PMAA) was synthesized and then hydrogenated in this work. The chain structure, phase behavior and thermal properties were characterized by 1H NMR, FTIR, XRD, DSC, TGA, etc., and the physicochemical and biomedical properties were investigated via fluorescence spectroscopy, TEM, DLS, loading and release of drug and MTT, and so on. The experimental results indicated that the hydrogenation led to the change in the chain aggregate structure of hydrophobic HTPB blocks and the formation of more stable spherical core-shell micelle aggregates, and the critical micelle concentration decreased from 41.8 mg L−1 before hydrogenation to 4.4 mg L−1 after hydrogenation. The hydrogenated block copolymer micelle aggregates exhibited pH-triggered response, and could entrap twice as much hydrophobic drug as the unhydrided counterparts and the encapsulation efficiency was significantly improved, which makes them fine to meet the requirements for drug carriers. Therefore, the hydrogenated PMAA-b-HTPB-b-PMAA copolymer micelles as drug target release carriers can be well used in the field of prevention and treatment of cancers.

研究领域: 材料科学 · 生物医学工程 · 药学
✓ 已验证 DOI PubMed 高影响因子
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Polymer Chemistry · 2013 ·Vol. 4 ·期 8 ·2489-2495 · IF 5.231

Template synthesis of PMAA@chitosan hollow nanorods for docetaxel delivery

Yajuan Sun,Weibing Dong,Huiyuan Wang,Yongzhuo Huang,Huike Gu,Victor C. Yang,Junbo Gong

Nanorods are capable of enhanced intracellular delivery and prolonged blood circulation over their spherical counterparts, and thus can be used as unmatched drug carriers for cancer chemotherapy. An innovative method was developed to synthesize size-tunable, PMAA@chitosan-based, hollow polymeric nanorods for intracellular delivery, by using mesoporous silica nanorod templates. The morphology of the polymeric hollow nanorods was examined by TEM and FT-IR spectra, which indicated a homogeneous three-dimensional structure. An uptake study using human lung carcinoma A-549 cell lines revealed highly efficient cell internalization of the FITC-labeled nanorods, suggesting the potential of utilizing these nanorods as carriers in achieving effective intracellular drug delivery. Cell viability studies of the docetaxel-loaded nanorods yielded consistent results, as the drug-loaded nanorods produced a significantly higher inhibition of the growth of A-549 tumor cells when compared with treatment by free docetaxel. Overall, this preliminary in vitro investigation sheds light on the use of prepared hollow polymeric nanorods for drug delivery applications.

研究领域: 生物材料学 · 药剂学 · 肿瘤学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2018 · IF 3.141

UiO-66-NH2@PMAA: A Hybrid Polymer–MOFs Architecture for Pectinase Immobilization

Yan Li,Jiangtao Liu,Kehu Zhang,Lei Lei,Zhongli Lei

A hybrid polymer–MOFs architecture UiO-66-NH2@PMAA was synthesized by tethering polymethacrylic acid (PMAA) onto the surface of the metal–organic frameworks UiO-66-NH2, and it was further employed for pectinase immobilization by electrostatic interactions. The hybrid architecture was prepared through a combination of atom transfer radical polymerization (ATRP), click chemistry and postsynthetic modification (PSM). The optimal immobilization parameters were at 25 °C and pH 4.0 with 10 U/mL of pectinase for 2 h, under which pectinase showed the highest enzymatic activity (1.215 U/mg) and protein loading (448.5 mg/g), respectively. Compared with free pectinase, the immobilized was found to exhibit higher pH, thermo, and storage stability. Additionally, the immobilized pectinase had remarkable reusability, the residual activity reached as high as 81% after 8 cycles continuously. Meanwhile, the desorption of immobilized pectinase can be achieved by changing pH values of the medium. Obviously, the UiO-66-NH2@PMAA with attractive properties is highly promising for enzyme immobilization.

研究领域: 生物化学 · 材料科学
✓ 已验证 DOI 高影响因子
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International Journal of Bioprinting · 2023 · IF 8.4

DLP-printed GelMA-PMAA scaffold for bone regeneration through endochondral ossification

Jianpeng Gao,Hufei Wang,Ming Li,Zhongyang Liu,Junyao Cheng,Xiao Liu,Jianheng Liu,Xing Wang,Licheng Zhang

Intramembranous ossification (IMO) and endochondral ossification (ECO) are two pathways of bone regeneration. The regeneration of most bone, such as limb bone, trunk bone, and skull base bone, mainly occurs in the form of endochondral ossification, which has also become one of the effective ways for bone tissue engineering. In this work, we prepared a well-structured and biocompatible methacrylated gelatin/polymethacrylic acid (GelMA/PMAA) hydrogel by digital light processing (DLP) printing technology, which could effectively chelate iron ions and continuously activate the hypoxia-inducible factor-1 alpha (HIF-1α) signaling pathway to promote the process of endochondral ossification and angiogenesis. The incorporation of PMAA endowed the hydrogel with remarkable viscoelasticity and high efficacy in chelation of iron ions, giving rise to the activation of HIF-1α signaling pathway, improving chondrogenic differentiation in the early stage, and facilitating vascularization in the later stage and bone remodeling. Therefore, the findings have significant implications on DLP printing technology of endochondral osteogenesis induced by the iron-chelating property of biological scaffold, which will provide an effective way in the development of novel bone regeneration.

CAS / MDL: 79-41-4
研究领域: 组织工程 · 生物材料 · 再生医学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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RSC Advances · 2016 ·Vol. 6 ·期 63 ·58218-58225 · IF 3.289

PMAA-based RAFT dispersion polymerization of MMA in ethanol: conductivity, block length and self-assembly

Henmei Ni,Junxiu Liu,Kai Shi,Min Wu,Yadong Yang,Lijuan Zhang

The reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization of methyl methacrylate (MMA) was carried out in ethanol using polymethacrylic acid (PMAA)–4-cyanopentanoic acid dithiobenzoate (CADB) (degree of polymerization = 30, 122 and 450) as a macro chain transfer agent (CTA) and 2,2′-azobis(2,4-diemthyl valeronitrile) (V-65) as an initiator. In contrast to the random copolymerization systems, a dramatic increase of conductivity during the initial stage of RAFT polymerization was observed. It was confirmed that the conductivity resulted from the charged solvophobic blocks of soluble diblock copolymers, strongly dependent on the chain length of PMAA-CTA and PMMA. Objects of PMAA-b-PMMA were prepared by three methods, i.e. the polymerization-, temperature- and ion-induced self-assembly. The procedure of self-assembly commonly resulted in a dramatic decrease of conductivity. All results indicated that the electrostatic interaction played a role in the process of self-assembly, rather than just the solvophobic interaction of PMMA blocks in ethanol.

CAS / MDL: 79-41-4 80-62-6
研究领域: 材料科学 · 高分子化学
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JOURNAL OF BIOMATERIALS SCIENCE-POLYMER EDITION · 2022 · IF 3.682

Preparation, stimuli-response performance of HPC-PMAA/PpIX nanogels and their application in photodynamic therapy

Chengyan Zhao,Qiusheng Song,Lin Zhu,Haihong Ma

In the present study, a novel nanogel of HPC-PMAA/PpIX with thermo- and pH sensitive performance and its application in cancer photodynamic therapy is reported. HPC-PMAA/PpIX nanogels were prepared by free radical polymerization method with HPC as template, hydroxypropyl cellulose (HPC), methyl acrylic acid (MAA), protoporphyrin IX (PpIX) and N,N′-methylene bisacrylamide (BIS) as raw materials. The as-prepared nanogels were characterized by Fourier transform infrared (FTIR), photoluminescence (PL) and UV–visible spectrophotometer (UV–vis), dynamic light scattering (DLS) and transmission electron microscopy (TEM). PL and UV–vis spectra demonstrate that PpIX is incorporated into HPC-PMAA by covalent bonds, and its aggregation is prevented. Moreover, the as-prepared nanogels can be dispersed in water over 1 week, significant singlet oxygen can be produced under irradiation of laser. With tumor cell of HepG2 as model cell, the nanogels are biocompatible with cell viability of >85% even at high concentrations of the PpIX in vitro. In addition, the HPC-PMAA/PpIX nanogels show photo-dependent toxicity in the concentration range of 10 µg/mL of PpIX, suggesting that HPC-PMAA/PpIX nanogels have potential for the treatment of photodynamic therapy (PDT).

研究领域: 生物医学工程 · 癌症治疗 · 材料科学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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ACS Applied Materials & Interfaces · 2021 · IF 9.229

Preparation of Fe3O4@PMAA@Ni Microspheres towards the Efficient and Selective Enrichment of Histidine-Rich Proteins

Yang Wang,Yingying Wei,Pengcheng Gao,Si Sun,Qian Du,Zhifei Wang,Yong Jiang

Magnetic material is considered to as a major concern material for the enrichment of histidine-rich proteins (His-proteins) via metal-ion affinity. In this work, magnetic polymer microspheres with core–shell structure (Fe3O4@PMAA@Ni) were successfully prepared via reflux-precipitation polymerization followed by in situ reduction and growth of Ni2+. The obtained Ni nanofoams with flower-like structure and uniform pore size (3.34 nm) provided numerous binding sites for His-proteins. The adsorption performance of Fe3O4@PMAA@Ni microspheres for His-proteins was estimated via selectively separating bovine hemoglobin (BHb) and bovine serum albumin (BSA) from a matrix composed of BHb, BSA, and lysozyme (LYZ). The results indicated that Fe3O4@PMAA@Ni microspheres could efficiently and selectively separate His-proteins from the matrix, with a maximum adsorption capacity of ∼2660 mg/g for BHb. Moreover, Fe3O4@PMAA@Ni microspheres exhibited good stability and recyclability for BHb separation over seven cycles. Therefore, this work reported a novel and facile strategy to prepare core–shell Fe3O4@PMAA@Ni microspheres, which was promising for practical applications of His-protein separation and purification in proteomics.

研究领域: 生物化学 · 蛋白质组学 · 材料科学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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Journal of Materials Chemistry B · 2020 ·Vol. 8 ·期 6 ·1266-1276 · IF 5.344

PAMAM–PMAA brush-functionalized magnetic composite nanospheres: a smart nanoprobe with tunable selectivity for effective enrichment of mono-, multi-, or global phosphopeptides

Lingzhu Yu,Bin Luo,Zhiyu Li,Jia He,Fang Lan,Yao Wu

Selective capture of mono-, multi- or global phosphopeptides is significant for the in-depth study of protein kinase or phosphatase signal transduction pathways. However, this study is largely restricted because of the lack of versatile affinity materials with high enrichment capacity and tunable selectivity. Here, we prepared a smart nanoprobe for the selective enrichment of mono-, multi- or global phosphopeptides by introducing polyamidoamine dendrimer (PAMAM)-grafted poly(methacrylic acid) (PMAA) brushes to modified magnetic composite nanospheres (denoted as Fe3O4@PDA@PMAA@PAMAM). The practicability of the prepared nanospheres for phosphopeptide enrichment was investigated by using model proteins (α-casein and β-casein) and complex biological samples (nonfat milk and human saliva). The extremely abundant amine groups of PAMAM–PMAA brushes and superparamagnetism of the Fe3O4 core endowed the composite nanospheres with high detection sensitivity (1 fmol μL−1), excellent selectivity (1 : 500 molar ratios of β-casein/BSA) and high recyclability (five cycles) towards phosphopeptides. Additionally, based on the tunable bonding ability of the nanospheres towards phosphopeptides with different phosphorylation sites, selective enrichment of mono-, multi- or global phosphopeptides was realized by modulating buffer polarity and acidity, making them ideal new nanoprobes for comprehensive phosphoproteome analysis.

研究领域: 生物化学 · 纳米医学 · 蛋白质组学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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JOURNAL OF NANOBIOTECHNOLOGY · 2021 ·Vol. 19 ·期 1 ·1-13 · IF 10.435

MSCs-engineered biomimetic PMAA nanomedicines for multiple bioimaging-guided and photothermal-enhanced radiotherapy of NSCLC

Yin Yipengchen,Li Yongjing,Wang Sheng,Dong Ziliang,Liang Chao,Sun Jiaxin,Wang Changchun,Chai Rong,Fei Weiwei,Zhang Jianping,Qi Ming,Feng Liangzhu,Zhang Qin

Background The recently developed biomimetic strategy is one of the mostly effective strategies for improving the theranostic efficacy of diverse nanomedicines, because nanoparticles coated with cell membranes can disguise as “self”, evade the surveillance of the immune system, and accumulate to the tumor sites actively. Results Herein, we utilized mesenchymal stem cell memabranes (MSCs) to coat polymethacrylic acid (PMAA) nanoparticles loaded with Fe(III) and cypate—an derivative of indocyanine green to fabricate Cyp-PMAA-Fe@MSCs, which featured high stability, desirable tumor-accumulation and intriguing photothermal conversion efficiency both in vitro and in vivo for the treatment of lung cancer. After intravenous administration of Cyp-PMAA-Fe@MSCs and Cyp-PMAA-Fe@RBCs (RBCs, red blood cell membranes) separately into tumor-bearing mice, the fluorescence signal in the MSCs group was 21% stronger than that in the RBCs group at the tumor sites in an in vivo fluorescence imaging system. Correspondingly, the T 1 -weighted magnetic resonance imaging (MRI) signal at the tumor site decreased 30% after intravenous injection of Cyp-PMAA-Fe@MSCs. Importantly, the constructed Cyp-PMAA-Fe@MSCs exhibited strong photothermal hyperthermia effect both in vitro and in vivo when exposed to 808 nm laser irradiation, thus it could be used for photothermal therapy. Furthermore, tumors on mice treated with phototermal therapy and radiotherapy shrank 32% more than those treated with only radiotherapy. Conclusions These results proved that Cyp-PMAA-Fe@MSCs could realize fluorescence/MRI bimodal imaging, while be used in phototermal-therapy-enhanced radiotherapy, providing desirable nanoplatforms for tumor diagnosis and precise treatment of non-small cell lung cancer.

研究领域: 纳米技术 · 生物医学工程 · 肿瘤学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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COLLOID AND POLYMER SCIENCE · 2020 ·Vol. 299 ·期 4 ·663-674 · IF 1.536

Preparation of zwitterionic microspheres of PDMAEMA-b-PMAA by RAFT dispersion polymerization in alcohol, their pH-sensitivity in water, and self-assembly in KCl solution

Xia Yunfei,Xu Xiuhang,Yu Haihua,Zhou Chuan,Nie Zhenzhou,Yang Jianfeng,Qian Jiajia,Ni Henmei

Zwitterionic microspheres of poly2-(dimethylamino) ethyl methacrylate (PDMAEMA) block polymethacrylic acid (MAA) were prepared by RAFT dispersion polymerization in alcohols. 4-Cyano-4-(phenylcarbonothioylthio) pentanoic acid (CPDB) was used as the RAFT agent. 2,2′-Azobis(2,4-dimethyl) valeronitrile (V65) was used as the initiator, and PDMAEMA-CPDB was used as the macro-chain transfer agent (CTA). 1 HNMR was applied to determine the polymerization degrees of both PDMAEMA-CTA and PDMAEMA-b-PMAA. SEM, dynamic light scattering (DLS), and small-angle X-ray diffraction (SAX) were employed to characterize the microspheres. It was observed that the polarity of alcohols impacted the partition of MAA and V65 between the mini-droplets of PDMAEMA-CTA/MAA complexes and the continuous phase, thereby affected on the diameters of microspheres, the total conversion of MAA, and the polymerization degree of PMAA in the copolymers. For example, in methanol, the smallest diameter and polymerization degree of PMAA in the block copolymers were obtained, whereas the total conversion of MAA of the RAFT polymerization system was the highest. Most of RAFT polymerization of MAA occurred nearby PDMAEMA-CTA chains; thus, PDMAEMA-CTA acted as a template to regulate the length of PMAA in the copolymers. pH-sensitive characteristics of microspheres were dependent to the extra length of PDMAEMA-CTA, i.e., the difference of lengths between two blocks. When the length of PMAA was too short, e.g., PDMAEMA 600 -b-PMAA 87 , or the length of PMAA was closed to that of PDMAEMA, e.g., PDMAEMA 79 -b-PMAA 93 and PDMAEMA 102 -b-PMAA 131 , the amphoteric characteristics of microspheres disappeared. The self-assembly behavior of diblock copolymers in KCl alcohol-water solution was also determined by the extra length of PDMAEMA. Microspheres turned into nanofibers or nano-ribbons, but for PDMAEMA 600 -b-PMAA 87 , the microspheres maintained their original spheric morphology. These results indicated that the charge-screening effects of salts played the key roles in the self-assembly. Graphical abstract

CAS / MDL: 79-41-4
研究领域: 高分子化学 · 材料科学
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2013 · IF 2.108

Dual-responsive polyacrylate copolymer micelles with PMAA and PNIPAAm graft brushes: Physicochemical properties and prednisone release

Yan-Ling Luo,Rui-Juan Huang,Li-Li Zhang,Feng Xu,Ya-Shao Chen

A thermo- and pH-stimuli-responsive brush-shaped graft copolymer based on macromonomers acrylate terminated PMAA–CH=CH 2 and PNIPAAm–CH=CH 2 was synthesized, which is composed of poly(methacrylic acid) (PMAA) and poly( N -ispropylacrylamide) (PNIPAAm) as graft brushes, named PMAA- b -PNIPAAm. The copolymers can self-assemble to form spherically-shaped core-shell nanostrucrued micelles in different media, with the critical micelle concentration (CMC) in aqueous solution from 9.24 to 32.81   mg   L −1 , and the hydrodynamic diameters varying with pH and temperature, from 120 to 195   nm. The resultant nanoscale copolymer micelles exhibited pH-triggered thermoresponsive behavior, with low critical solution temperature (LCST) about 38.2–47.5   °C. The polymer micelle nanoparticles were observed to be stable under simulated physiological conditions. The cytotoxicity studies by MTT assay and in vitro prednisone drug release demonstrated that the PMAA- b -PNIPAAm copolymer micelles were not directly toxic to L929 mouse embryonic fibroblasts and the in vitro release behavior under various physiological environments depended upon pH and temperature change. Therefore the as-prepared brush-shaped graft copolymer micelle nanoparticles may serve as a promising “intelligent” drug delivery carrier.

研究领域: 材料科学与工程 · 生物医学工程 · 药物递送系统
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Materials Today Communications · 2023 · IF 3.8

Water soluble β-CD-PMAA/PMAm/PHEMA-Coumarin macromolecular fluorescent probes prepared via RAFT method and their sensing ability to Fe3+/Fe2+ and Cu2+ ions

Siyuan Zhang,Xinjian Cheng

Developing water-soluble fluorescent probes has important scientific and practical significance. In this work, coumarin derivatives bearing -OH were obtained through the classical Knoevenagel reaction firstly. Secondly, -C C- on allyl bromide was introduced into coumarin by Williamson ether formation method. Thirdly, hydrazine hydrate was added to the coumarin derivatives, a polymerizable small molecular coumarin fluorophore containing probe was obtained successfully. And, the -COOH on di-thioester underwent an esterification reaction with –OH groups on β-cyclodextrin(β-CD) to prepare oligomer based reversible addition-fragmentation chain transfer(RAFT) reagents. Finally, three copolymer probes β-CD-PMAA-Coumarin, β-CD-PMAm-Coumarin, and β-CD-PHEMA-Coumarin were prepared via RAFT polymerization , in which C C-coumarin was used as the functional monomer and methacrylamide(MAm)/methacrylic acid (MAA)/hydroxyethyl methacrylate (HEMA) as the main monomers. The MALDI-TOF mass tests showed that the macromolecular level probes were successfully prepared. These polymer probes have molecular weights up to 5.4 kDa and have narrow molecular weight distributions (PDI≤1.31). With the assistance of water-soluble long-chained PMAm/PMAA/PHEMA and hydrophilic β-CD, the coumarin containing macromolecular fluorescent probes could be dissolved in water readily. These water soluble polymer fluorescent probes could recognize Fe 3+ /Fe 2+ and Cu 2+ ions with high sensitivity. The detection limit of Fe 3+ could be as low as 0.34 μM. This study successfully developed a promising technique for producing highly selective, fully water-soluble fluorescent macromolecular probes.

研究领域: 化学 · 材料科学 · 分析化学
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