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COMPOSITES PART B-ENGINEERING · 2024 · IF 12.7

One-pot solvent-free green strategy to fabricate ultra-efficient polyphosphoester flame retardant for Poly(Lactic acid)

Zhicheng Bai,Feixiang Yin,Jiahao Shen,JinJia Xu,Fengqing Chen,Teng Huang,Hufeng Li,Dan Xie,Yi An,Wenbiao Zhang,Jinfeng Dai

Tremendous attention has been dedicated to crafting eco-friendly flame retardants with excellent comprehensive performance via green means. Herein, a novel ultra-efficient polyphosphoester (PPE) flame retardant was synthesized via a facile one-pot method of solid-phase polycondensation reaction. PPE was then employed as a multifunctional additive for high-performance poly (lactic acid) (PLA). Benefiting from the dual-phase flame-retardant effect, the resultant PLA composite with merely 0.5 wt% PPE exhibited a desired limiting oxygen index (LOI) value of 26.1 %, and a satisfactory V0 rating of UL-94 (1.6 mm) with well-preserved mechanical properties. Due to the nucleating effect of PPE on PLA, the mechanical properties and crystallization ability of the PLA composites were both gradually enhanced as PPE content increased from 0.3 to 1.5 wt%. The designed ultra-efficient approach, enhancing fire safety and mechanical properties simultaneously at a low content, lays a foundation of an affordable, eco-friendly, and versatile flame retardant for potential applications of PLA.

CAS / MDL: 5593-70-4 839-90-7
研究领域: 材料科学 · 绿色化学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2023 · IF 4.2

Treatment of Organophosphorus Esters Waste by CeO2: Efficient Degradation with Simultaneous Phosphorus Immobilization

Xuqian Wang,Wendan Zheng,Wenhua Tong,Aimin Zhang,Yongkui Zhang,Yabo Wang

Organophosphorus esters (OPEs) are important chemicals functioning as extractants, plasticizers, flame retardants, solvents, additives, etc., and are also recognized as hazardous organic liquids generated from industrial processes. Herein, we developed a CeO2-catalyzed degradation with simultaneous phosphorus immobilization technology to treat typical OPE solvents. Under the investigated reaction conditions of a temperature of 180 °C, a reaction time of 3 h, and a dosage of ball-milled CeO2 of 19.8 g mL–1 of the OPE, the model pollutant of tributyl phosphate (TBP) was efficiently degraded with phosphorus immobilization efficiency near 100%. Meanwhile, the mineralization efficiency of TBP was also as high as 98%, which was reflected by the chemical oxygen demand change of liquid products. Gaseous products generated from CeO2-catalyzed TBP degradation could also fulfill the requirements of an environmental standard. Further mechanism studies indicated that the surface oxygen vacancy in CeO2 induced the in situ formation of superoxide radicals, which dominated TBP degradation. During catalytic degradation, the P-containing species were mainly immobilized as cerium phosphate, while the hydrocarbon chains of TBP were degraded into small molecules and finally mineralized into inorganic species. The developed CeO2-catalyzed OPE degradation approach was also applicable to aromatic and halogenated OPEs, i.e., tricresyl phosphate and tris(2-chloroethyl) phosphate. This study provided a possible alternative for waste treatment of the waste of OPEs with low environmental risks.

研究领域: 环境科学 · 化学工程
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ACS Applied Materials & Interfaces · 2014 · IF 5.9

Effect of Hydrophobicity of Core on the Anticancer Efficiency of Micelles as Drug Delivery Carriers

Chun-Yang Sun,Yin-Chu Ma,Zi-Yang Cao,Dong-Dong Li,Feng Fan,Jun-Xia Wang,Wei Tao,Xian-Zhu Yang

Recently, micelles, which are self-assembled by amphiphilic copolymers, have attracted tremendous attention as promising drug delivery systems for cancer treatment. Thus, the hydrophobic core of the micelles, which could efficiently encapsulate small molecular drug, will play a significant role for the anticancer efficiency. Unfortunately, the effect of hydrophobicity of micellar core on its anticancer efficiency was rarely reported. Herein, the amphiphilic diblock polymers of poly(ethylene glycol) and polyphosphoester with different side groups (butyl, hexyl, octyl) were synthesized to tune the hydrophobicity of the micellar core. We found that the in vitro cytotoxicity of the DOX-loaded micelles decreased with the increasing hydrophobicity of micellar core due to the drug release rate. However, following systemic delivery, the DOX-loaded micelles with the most hydrophobic core exhibited the most significant inhibition of tumor growth in a MDA-MB-231 tumor model, indicating the importance of hydrophobicity of core on the antitumor efficacy of drug delivery systems.

研究领域: 药学 · 肿瘤学
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CELLULOSE · 2021 ·Vol. 28 ·期 5 ·3201-3214 · IF 5.044

A novel biomass vitamin B6-based flame retardant for lyocell fibers

Su Xiaowei,Cheng Chunzu,Zheng Yunbo,Liu Xiaohui,Ren Yuanlin,He Ju,Lin Shenggen,Cheng Bowen

A biomass vitamin B6-based flame retardant, ammonium salt of pyridoxine phosphoric ester acid (ASPPEA) was synthesized and used for modification of lyocell fibers. FTIR, XPS and EDX analyses indicated that lyocell fibers had been successfully grafted with ASPPEA. The ASPPEA improved the char-forming ability, as evidenced by the increase of the char residue (51 wt%) of ASPPEA-treated lyocell fibers. The limiting oxygen index (LOI) value of ASPPEA-treated lyocell fabrics increased up to 48.3%. After 450 min washing, the LOI value remained 30.8%, thus demonstrating the flame retardant durability. The total heat release of ASPPEA-treated lyocell fabrics decreased by 82.5%. During the pyrolysis, the ASPPEA decomposed to produce acidic substances which promoted the dehydration and char formation of lyocell fibers, thus blocked the exchange of heat and flammable gas. This research proposes a novel application of vitamin B6 to impart lyocell fibers with flame retardancy.

CAS / MDL: 461-58-5
研究领域: 材料科学 · 生物质化学
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CHEMICAL RESEARCH IN CHINESE UNIVERSITIES · 2019 ·Vol. 35 ·期 2 ·340-344 · IF 1.071

Functionalized Polyphosphoester via Living Ring-opening Polymerization and Photochemical Thiol-ene Click Reaction

Wang Ying,Wang Qiliao,Hou Liman,Zhou Mingdong,Dong Dewen,Zhang Ning

Poly(ethylene phosphonate) was synthesized via the living ring-opening polymerization of cyclic phosphonate monomer catalyzed by organocatalyst. The pendant vinyl functionalities were employed to perform the photochemical click reactions with thiols. We demonstrated that both small thiol molecules and macromolecular thiols could be efficiently coupled into the PPE side chains, enabling the rapid and efficient functionalization of polyphosphoesters( PPE).

CAS / MDL: 622-08-2
研究领域: 高分子化学 · 材料科学
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BIOMACROMOLECULES · 2019 · IF 5.667

Synthesis of an Oxidation-Sensitive Polyphosphoester Bearing Thioether Group for Triggered Drug Release

Jihong Wang,Dongdong Li,Wei Tao,Yang Lu,Xianzhu Yang,Jun Wang

In this work, novel amphiphilic diblock copolymers of polyethylene glycol and polyphosphoester with pendant thioether groups, denoted as mPEG-b-PMSPEP, were synthesized through the ring-opening polymerization of functionalized cyclic phosphoester monomer using methoxy poly(ethylene glycol) and Sn(Oct)2 as the macroinitiator and catalyst, respectively. The successful synthesis was confirmed by 1H, 13C, 31P nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). These amphiphilic block copolymers self-assembled spontaneously in the aqueous solution, and the formed nanoparticles were sensitive to the oxidation that induced the hydrophobic to hydrophilic transition for its PMSPEP core under triggering of H2O2 and the subsequent dissociation of the nanoparticles. In addition, the reactive oxygen species (ROS) generated by light and the photosensitizer were also capable of carrying out the oxidation of these nanoparticles. Their oxidation profiles were systemically evaluated by 1H NMR. Finally, the mPEG-b-PMSPEP nanoparticles were used to coencapsulate the photosensitizer chlorin e6 (Ce6) and anticancer drug paclitaxel (PTX), achieving the photoaccelerated PTX release via oxidation of the nanoparticles by the generated ROS under light irradiation. Meanwhile, the in vitro cytotoxicity assays indicated that these nanoparticles coencapsulated with PTX and Ce6 showed a combined cell-killing effect toward MDA-MB-231 tumor cells, exhibiting great potential for drug delivery systems that realize the synergistic chemo-photodynamic therapy for cancer treatment.

CAS / MDL: 505-10-2
研究领域: 生物材料 · 药剂学 · 肿瘤治疗
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Materials Today Chemistry · 2018 · IF 0

ROS-responsive selenium-containing polyphosphoester nanogels for activated anticancer drug release

Yan Zhang,Chuan Ma,Sihang Zhang,Chao Wei,Ying Xu,Wei Lu

Nowadays, the stability and on-demand release of drug carriers are still to be solved. To meet the demand of these issues, we developed a reactive oxygen species (ROS) responsive selenium-containing polyphosphoesters nanogel (PSeP) by a facile one-step ring-opening polymerization of the novel monomer 4-selenoctane-1,8-diyl bis(propylphosphatelane) (Se-COP) with polyethylene glycol (mPEG) employed as the macroinitiator. Their structure was confirmed by NMR, FT-IR and GPC. The crosslinked core-shell structure imparted the nanogels with excellent dimensional stability according to the dynamic light scattering (DLS) and transmission electron microscopy (TEM). Moreover, the selenide groups endowed the nanogels with rich ROS responsiveness when subjected to the stimuli of H 2 O 2 , thus the drug-loaded PSeP nanogels displayed swollen behaviors leading to an activated doxorubicin hydrochloride (DOX · HCl) release. The release mechanisms fitted by the Ritger-Peppas power-law model also proved the swollen release process. MTT assays exhibited that the PSeP nanogels were nontoxic up to a tested concentration of 50 μg mL −1  by A549 and HEK293, and the DOX-loaded PSeP had a high anti-cancer behaviour against A549 cancer cells. Additionally, these nanogels possessed enhanced intracellular drug release by CLSM . Therefore, these results highlighted that the selenium-containing polyphosphoesters nanogels could be a potential platform for the ROS-sensitive drug delivery.

CAS / MDL: 6609-64-9 7782-49-2
研究领域: 生物材料学 · 药剂学 · 肿瘤学
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ACS Applied Materials & Interfaces · 2017 · IF 7.504

Polyphosphoester-Camptothecin Prodrug with Reduction-Response Prepared via Michael Addition Polymerization and Click Reaction

Xueqiong Du,Yue Sun,Mingzu Zhang,Jinlin He,Peihong Ni

Polyphosphoesters (PPEs), as potential candidates for biocompatible and biodegradable polymers, play an important role in material science. Various synthetic methods have been employed in the preparation of PPEs such as polycondensation, polyaddition, ring-opening polymerization, and olefin metathesis polymerization. In this study, a series of linear PPEs has been prepared via one-step Michael addition polymerization. Subsequently, camptothecin (CPT) derivatives containing disulfide bonds and azido groups were linked onto the side chain of the PPE through Cu(I)-catalyzed azidealkyne cyclo-addition “click” chemistry to yield a reduction-responsive polymeric prodrug P(EAEP-PPA)-g-ss-CPT. The chemical structures were characterized by nuclear magnetic resonance spectroscopy, gel permeation chromatography, Fourier transform infrared, ultraviolet–visible spectrophotometer, and high performance liquid chromatograph analyses, respectively. The amphiphilic prodrug could self-assemble into micelles in aqueous solution. The average particle size and morphology of the prodrug micelles were measured by dynamic light scattering and transmission electron microscopy, respectively. The results of size change under different conditions indicate that the micelles possess a favorable stability in physiological conditions and can be degraded in reductive medium. Moreover, the studies of in vitro drug release behavior confirm the reduction-responsive degradation of the prodrug micelles. A methyl thiazolyl tetrazolium assay verifies the good biocompatibility of P(EAEP-PPA) not only for normal cells, but also for tumor cells. The results of cytotoxicity and the intracellular uptake about prodrug micelles further demonstrate that the prodrug micelles can efficiently release CPT into 4T1 or HepG2 cells to inhibit the cell proliferation. All these results show that the polyphosphoester-based prodrug can be used for triggered drug delivery system in cancer treatment.

CAS / MDL: 818-61-1
研究领域: 材料科学 · 生物医学工程 · 肿瘤学
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JOURNAL OF INORGANIC BIOCHEMISTRY · 2017 · IF 3.348

Synthesis, crystal structure and hydrolysis activity of a novel heterobinuclear cobalt(ІІІ) sodium(І) Schiff base complex

Xin Li,Zihui Liu,Ying Xu,Dongfeng Wang

A novel heterobinuclear complex [CoNa(C 15 H 10 NO 4 F) 2 (CH 3 OH)] 2 with Schiff base (C 15 H 10 NO 4 F: 2-amino-4-fluorobenzoic acid-3-methoxysalicylaldehyde) was synthesized and characterized by IR and 1 H NMR spectroscopy, elemental analysis and single crystal X-ray diffraction. X-ray crystallography reveals that the cobalt atom is six-coordinated by two nitrogen atoms from –C N–, two carboxylate oxygen atoms and two hydroxyl oxygen atoms in different ligands, while the sodium atom is seven-coordinated by two methoxy oxygen atoms, two hydroxyl oxygen atoms in different ligands, two oxygen atoms in the same carboxylate and one oxygen atom of solvent methanol. The reaction results of the complex with the p -nitrophenylphosphate (pNPP) and the adenosine monophosphate (AMP) reveal that the complex can hydrolyze phosphoester bonds. Then the DNA-hydrolysis activity is studied experimentally and theoretically, indicating that the complex can effectively hydrolyze the pBR322 supercoiled plasmid DNA . The molecular docking technology predicts the best binding site and binding affinity between the complex and DNA, and then the catalytic mechanism of hydrolysis is supposed. The study results suggest that the Schiff base metal complex, as a potent artificial enzyme , may find its applications in catalytic hydrolysis and biotechnological areas.

研究领域: 配位化学 · 生物无机化学 · 催化化学
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Journal of Materials Chemistry B · 2025 · IF 5.7

3D Printed Polycaprolactone/Phosphoester-Modified Poly (amino acids)-Graphene Oxide Scaffold for Meniscal Regeneration

Zeping Yu,Fei Xing,Jianshu Li,Wenli Zhang,Hong Duan,Jian Li,Yan Xiong

Given the limited blood supply that results in the meniscus's poor self-healing ability, meniscal tissue engineering (MTE) scaffolds have emerged as an effective strategy for the treatment of meniscal injuries. However, the efficacy of mesenchymal stem cells (MSCs) is limited in the inflammatory state caused by chronic injuries, making it challenging for existing meniscal implants to promote meniscal regeneration and delay articular cartilage degeneration in an inflammatory environment. This study introduces a method to incorporate phosphoester (PE) units into the main chain of poly (amino acids) (PAAs) through ring-opening copolymerization, subsequently creating a copolymer with graphene oxide (GO) to yield phosphoester-modified poly (amino acids)-graphene oxide (P-P-GO). PCL/P-P-GO scaffolds were fabricated by blending P-P-GO with polycaprolactone (PCL) and employing 3D printing technology. The PAAs of P-P-GO scaffold provide a nutritious environment essential for MSC proliferation, migration, and differentiation, while the PE enhance the cell adhesion properties, with further improvements by GO. In vitro experiments have shown that the PCL/P-P-GO scaffold upregulates the expression of chondrogenic-specific genes and increase the production of collagen and glycosaminoglycans. Additionally, γ-aminobutyric acid of the scaffolds can suppress the secretion of inflammatory factors, induce M2 polarization of macrophages, and promote angiogenesis. In vivo studies using rabbit meniscectomy model have demonstrated that PCL/P-P-GO scaffolds can promote meniscal tissue regeneration and delay cartilage degeneration. After six months of implantation, the regenerated meniscus exhibited a structure and composition resembling natural meniscus, and the progression of osteoarthritis was significantly slowed. Compared to traditional cell-loaded scaffold strategy, PCL/P-P-GO scaffolds are easy to produce, cost-effective, and hold broad translational potential for the clinical treatment of meniscal injuries.

CAS / MDL: 105-60-2 24980-41-4
研究领域: 组织工程学 · 生物材料科学 · 再生医学
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Progress in Natural Science-Materials International · 2021 · IF 3.607

Renewable isosorbide-derived poly(phosphoester) for simultaneously enhanced flame-retardancy and mechanical property of polylactide

Xin Wang,Haoxin Niu,Wenwen Guo,Lei Song,Yuan Hu

Incorporating flame retardant fillers is the most efficient way to improve the fire resistance of polylactide (PLA). However, most flame retardant fillers result in deterioration of the mechanical property of PLA so far. Therefore, to create high-performance PLA materials combining excellent flame retardancy with superior mechanical properties remains highly attractive and challenging. In this study, a novel isosorbide-derived poly(phosphoester) (PIDI) was synthesized and used as a bio-based flame-retardant for PLA. The addition of PIDI showed a marginal effect on the change of the glass transition temperature of the PLA composites, but the crystallinity degree of the PLA composites was improved by the inclusion of PIDI. Benefitting from the improved crystallinity, the tensile strength, flexural strength, and impact strength of PLA composite containing 15 ​wt% PIDI was enhanced by 19.4%, 14.1%, and 36.9%, respectively, compared to the virgin PLA. With the addition of 20 ​wt% PIDI, the PLA composite showed an LOI value of 25.5% and a UL-94 V-0 rating in the vertical burning test. The flame retardant effect of PIDI was also demonstrated by a notable reduction (−46%) in the peak heat release rate (PHRR) of PLA composite containing 20 ​wt% PIDI. Such a renewable isosorbide-derived poly(phosphoester) is one of the promising candidates for PLA bio-composites with an outstanding balance between flame retardancy and intrinsic physical properties.

CAS / MDL: 97-65-4 652-67-5
研究领域: 材料科学 · 生物基材料 · 高分子化学
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JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY · 2013 ·Vol. 51 ·期 17 ·3667-3673 · IF 3.543

Cationic poly(ester-phosphoester)s: Facile synthesis and antibacterial properties

Weipu Zhu,Hong Du,Ying Huang,Shuai Sun,Ning Xu,Huagang Ni,Xia Cai,Xiaodong Li,Zhiquan Shen

Biodegradable poly(ester-phosphoester)s bearing multiple chloroethyl groups were synthesized facilely by the ring-opening copolymerization of 2-(2-chloroethoxy)-2-oxo-1,3,2-dioxaphospholane (CEP) and ε-caprolactone (CL) in the presence of lanthanum tris(2,6-di-tert-butyl-4-methylphenolate)s (La(DBMP) 3 ) as single-component catalyst under mild conditions. Then the quaternization reaction was carried out between the halide copolymers and a series of N,N -dimethyl alkylamines to give poly(ester-phosphoester)s containing ammonium groups with various charge density and alkyl chain length. The antibacterial properties of these cationic poly(esterphosphoester)s were evaluated by OD600 and zone of inhibition methods against gram-negative ( Escherichia coli ) and gram-positive ( Staphylococcus aureus ) bacteria. Cationic poly(esterphosphoester)s with long alkyl chain on the ammonium groups show excellent antibacterial activity for both gram-negative and gram-positive bacteria even with low charge density. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3667–3673

CAS / MDL: 107-21-1
研究领域: 高分子化学 · 生物医学材料 · 抗菌材料研究
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