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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2024 · IF 5.7

Hydroxamate-Containing Bisphosphonates as Fosmidomycin Analogues: Design, Synthesis, and Proherbicide Activity

Xin Wu,Zili Yang,Chunlin Song,Mengwei Bu,Weiguo Li,Jiang Duan,Guang-Fu Yang,Aidong Zhang

Fosmidomycin (FOS) is a natural product inhibiting the DXR enzyme in the MEP pathway and has stimulated interest for finding more suitable FOS analogues. Herein, two series of FOS analogue hydroxamate-containing bisphosphonates as proherbicides were designed, with bisphosphonate replacing the phosphonic unit in FOS while retaining the hydroxamate (BPF series) or replacing it with retro-hydroxamate (BPRF series). The BPF series were synthesized through a three-step reaction sequence including Michael addition of vinylidenebisphosphonate, N-acylation, and deprotection, and the BPRF series were synthesized with a retro-Claisen condensation incorporated into the reaction sequence. Evaluation on model plants demonstrated several compounds having considerable herbicidal activities, and in particular, compound 8m exhibited multifold activity enhancement as compared to the control FOS. The proherbicide properties were comparatively validated. Furthermore, DXR enzyme assay, dimethylallyl pyrophosphate rescue, and molecular docking verified 8m to be a promising proherbicide candidate targeting the DXR enzyme. In addition, 8m also displayed good antimalarial activities.

研究领域: 植物学 · 药理学 · 农业科学
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Journal of Orthopaedic Translation · 2025 · IF 7.8

Augmenting osteoporotic osseointegration through a temporal release nanocoating-based reversing dysregulated osteogenic microenvironment

Jiaxin Zhang,Haotian Bai,He Liu,Xiaonan Wang,Mingwei Xu,Guokun Zhang,Zexin Di,Xin Zhao,Jincheng Wang,Luquan Ren

Rationale Imbalances in the osteogenic–osteoclastic microenvironment hinder effective osseointegration between the prosthesis and host bone, which is a key factor contributing to the high incidence of prosthesis loosening and periprosthetic fractures in osteoporosis patients. Developing an implant interface that can reverse the dysregulated osteogenic microenvironment is an effective strategy to address this challenge. Methods A novel bioinspired interface with a spatial gradient structure was engineered by 3D-printed porous titanium alloy implants and hollow mesoporous silica nanoparticles coating. Apart from the bioinspired bone microstructure, the amine-functionalized nanocoating of the bioactive interface could also load and temporally sustain the zoledronic acid (ZOL) release. A series of in vitro experiments were carried out to characterize the bioactive interface and to clarify the regulation of osteogenic–osteoclastic balance by ZOL temporal release from the nanocoatings. Afterward, an osteoporotic model was utilized to validate the in vivo bioactive interface osseointegration effect. Results Based on the structural features and chemical properties of the bioactive interface, efficient ZOL loading was achieved. Additionally, the temporal release mechanism of ZOL through free diffusion and ionic bond ionization enabled long-term sustained release. Meanwhile, the early high-concentration local release of ZOL effectively inhibited osteoclast formation and activation in the microenvironment. As the ZOL release decreased over time, the focus shifted to promoting the process of bone formation, thereby reversing the dysregulated osteogenic microenvironment. According to this, we identified the optimal gradient concentration (10 -5 M) of the ZOL temporal release system that efficiently exerts bidirectional regulatory effects. Most notably, the spatial gradient structured interface loaded with this optimal concentration of ZOL (10 -5 M) significantly augmented osseointegration under in vivo osteoporotic conditions. Conclusion Overall, our study provides a novel nanocoating capable of temporally releasing ZOL to reverse the dysregulated osteogenic microenvironment, aiming to maintain the long-term stability of artificial prostheses for osteoporosis patients. The translational potential of this article This study validates the structure–performance-effect relationship of ZOL-releasing nanocoatings with a temporal release mechanism, providing a novel approach to addressing the high incidence of postoperative complications in osteoporotic patients undergoing prosthetic replacement.

研究领域: 生物医学工程 · 骨科 · 材料科学
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JOURNAL OF MEMBRANE SCIENCE · 2019 · IF 7.015

Organophosphonate draw solution for produced water treatment with effectively mitigated membrane fouling via forward osmosis

Chun Ding,Xuan Zhang,Shu Xiong,Liang Shen,Ming Yi,Boyang Liu,Yan Wang

In this study, an organophosphonate scale inhibitor, ethylenediamine tetra(methylenephosphonic acid) sodium salt (EDTMPA-Na) draw solution, was adopted for alleviating the membrane fouling in the forward osmosis (FO) application of produced water treatment. Compared with the typical NaCl draw solution, the employment of EDTMPA-Na draw solution can alleviate the membrane fouling effectively and therefore achieve a higher water recovery rate (60.6%) after a continuous 48-h test. And the mechanism of membrane fouling control with EDTMPA-Na draw solution has been systemically explored by varying the feed or draw solution compositions. The results turn out that the leakage of EDTMPA-Na draw solute to the feed solution can alleviate the formation of gypsum scales on the membrane surface effectively, ascribed to its excellent scale inhibition ability and the unique diffusion route of the draw solute (resulting in a relative higher concentration of EDTMPA-Na near the membrane surface) in FO process. And the alleviation of membrane scaling can further mitigate the accumulation of organic foulant on the FO membrane . This study may provide an efficient strategy for alleviating the membrane fouling in the FO application of produced water treatment.

CAS / MDL: 1429-50-1
研究领域: 环境科学 · 化学工程
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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Metal phosphonate sorbents: Enhancement of actinide sorption performance by gamma irradiation

Liang-ping Xiong,Mei Gu,Chu-ting Yang,Kai Lv,Feng-cheng Wu,Sheng Hu,Xing-gui Long

The effect of irradiation on actinide sorbents potentially employed in nuclear waste management, should be investigated to evaluate their feasibility in real-world applications. In this study, hafnium-amino trismethylene phosphonate (Hf-ATMP), which is a type of organic–inorganic hybrid sorbents for actinides, was exposed to 60 Co gamma rays, and the effects of ionising radiation on actinide sorption performance and its microstructure were investigated. Thereafter, the irradiation effect on other materials of this type was studied. The results revealed that the actinide sorption performance of Hf-ATMP was significantly enhanced by irradiation; the saturated Th(IV) sorption capacity of Hf-ATMP increased by 58.1% after irradiation with a dose of 2.4 MGy. The selectivity for actinides and the sorption performance for trace amounts of radioactive 239 Pu and 237 Np were also comparable to those of pristine Hf-ATMP. The structural characterisation of Hf-ATMP before and after irradiation indicated that the P-O–H groups in Hf-ATMP were converted into P-O-Hf groups upon irradiation. The pore volume and BET surface area of Hf-ATMP decreased, but the bulk chemical structure of Hf-ATMP was not damaged by gamma irradiation. Additionally, the enhancement of actinide sorption performance by gamma irradiation was observed with several other metal phosphonates. The results indicated the application potential of metal phosphonates as actinide sorbents in practical nuclear processes. Besides, this study opens a new door for improving the sorption performance of metal phosphonate sorbents using irradiation techniques.

研究领域: 核化学与技术 · 材料科学 · 放射化学
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CHINESE JOURNAL OF CATALYSIS · 2020 · IF 6.146

Hierarchical cobalt phenylphosphonate nanothorn flowers for enhanced electrocatalytic water oxidation at neutral pH

Mei-Rong Liu,Yang-Peng Lin,Kai Wang,Shumei Chen,Fei Wang,Tianhua Zhou

Cobalt-based phosphate/phosphonates are a class of promising water oxidation catalysts at neutral pH. Herein, we reported a facile hydrothermal synthesis of various nanostructured cobalt phenylphosphonates. It is found that the number of hydroxyl group of structure-directing reagent is crucial for the construction of 3D hierarchical structures including hierarchical nanosheet flower-like assemblies and nanothorn microsphere. These samples were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, infrared, and X-ray photoelectron spectroscopy techniques. They can act as highly efficient electrocatalysts for the oxygen evolution reaction at neutral pH. Among these, hierarchical cobalt phenylphosphonate nanothorn flowers present excellent performance, affording a current density of 1 mA cm −2 required a small overpotential of 393 mV. This work offers a new clue to develop high-performance metal phosphonate/phosphate catalysts toward electrochemical water oxidation.

研究领域: 材料科学 · 电化学
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E-POLYMERS · 2023 ·Vol. 23 ·期 1 · IF 3.7

Copper phenyl phosphonate for epoxy resin and cyanate ester copolymer with improved flame retardancy and thermal properties

Zhilin Cao,Changxin Ren,Zhengzhou Wang

Epoxy resin (EP)/cyanate ester (CE) copolymer, an important structural material with high temperature resistance and low dielectric constant in aerospace, microelectronics, and related fields, is still of great flammability danger. In this work, copper phenyl phosphonate (CuPP), a flame retardant used in EP/CE copolymer was synthesized by the reaction of phenyl phosphonic acid and copper nitrate trihydrate. The fire and thermal behavior of EP/CE/CuPP composites were studied in detail. The results suggested that the UL-94 rating and limiting oxygen index of EP/CE composite with 5 wt% CuPP (EP/CE/CuPP5) reach V-1 level and 30.6%, respectively. Compared with pure EP/CE copolymer, the peak heat release rate and total heat release values of EP/CE/CuPP5 decreased by 34.5% and 18.9%, respectively. The glass transition temperature of EP/CE/CuPP composite is higher than that of pure EP/CE copolymer, suggesting that the fire-retardant composite has higher work temperature and better heat resistance.

CAS / MDL: 1571-33-1
研究领域: 材料科学 · 化学工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Aminophosphonate CuO nanocomposites for uranium(VI) removal: Sorption performance and mechanistic study

Enas A. Imam,Ahmed I Hashem,Ahmad A. Tolba,Mohammad G. Mahfouz,Ibrahim El-Tantawy El-Sayed,Hamada B. Hawash,Rana R. Neiber,Hamed I. Mira,Ahmed A. Galhoum,Eric Guibal

Two aminophosphonate matrices (mono-aminophopshonate, MAP, and bi-aminophosphonate, BAP) are synthesized, varying the molar proportions of three precursors (thiocarbazide, p-phthalaldehyde, and triphenylphosphite). Nano-composites (CuO-MAP and CuO-BAP) are successfully elaborated by impregnation of the matrices with copper sulfate solution before processing to in situ precipitation of copper in alkaline solution (simultaneous partial Cu reduction). The sorbents are characterized using: TEM, XRD, elemental analysis, SEM-EDX, BET, titration (pH PZC ), XPS and FTIR analyses. Uranium sorption properties are compared for the different sorbents through the study of pH effect (optimum close to 4.5), the uptake kinetics (equilibrium reached in 60 min) and sorption isotherms. Uptake kinetics are finely fitted by the pseudo-second order rate equation (and the resistance to intraparticle diffusion). The sorption isotherms are modeled by the Langmuir equation with maximum sorption capacity (mmol U g −1 ) decreasing according to CuO-BAP(1.15) ≫ CuO-MAP(0.80) > BAP(0.74) ≫ MAP(0.50). The enhanced textural properties and the increase in the density of sorption sites (probably completed by a better steric arrangement for improved reactivity) may explain this ranking. The sorption is endothermic: sorption capacity and affinity coefficient increase with temperature. Uranium is readily desorbed from loaded-sorbents (efficiency > 98 %) using either HCl (0.2 M) solution or acidified urea (0.25 M) solution (pH 2.5) for aminophosphonate matrices and nano-composites, respectively. The type of sorbent does not affect the stability at recycling: at the sixth cycle, the loss in sorption and desorption performances varies by 6.2–7 % and 4.2–4.9 %, respectively. CuO-BAP sorbent shows high potential for uranium recovery from complex acid ore leachate. The broad spectrum of bound metals does not allow producing a pure yellow cake after ammonia precipitation of eluate (containing up to 15–22 % impurities).

研究领域: 环境科学 · 材料科学
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WATER RESEARCH · 2023 · IF 12.8

Complexation-based selectivity of organic phosphonates adsorption from high-salinity water by neodymium-doped nanocomposite

Chenhao Ni,Ningyi Chen,Jiahui He,Meilan Pan,Xianhua Wang,Bingjun Pan

Organic phosphonates have been widely used in various industries and are ubiquitous in wastewaters, and efficient removal of phosphonates is still a challenge for the conventional processes because of the severe interferences from the complex water constitutions. Herein, an Nd-based nanocomposite (HNdO@PsAX) was fabricated by immobilizing hydrated neodymium oxide (HNdO) nanoparticles inside a polystyrene anion exchanger (PsAX) to remove phosphonates from high-salinity aqueous media. Batch experiments demonstrated that HNdO@PsAX had an excellent adsorption capacity (∼90.5 mg P/g-Nd) towards a typical phosphonate (1-hydrox-yethylidene-1,1-diphosphonic acid, HEDP) from the background of 8 g/L NaCl, whereas negligible HEDP adsorption was achieved by PsAX. Attractively, various coexisting substances (humic acid, phosphate, citrate, EDTA, metal ligands, and anions) exerted negligible effects on the HEDP adsorption by HNdO@PsAX under high salinity. FT-IR and XPS analyses revealed that the inner-sphere complexation between HEDP and the immobilized HNdO nanoparticles is responsible for HEDP adsorption. Fixed-bed experiments further verified that HNdO@PsAX was capable of successively treating more than 4500 bed volumes (BV) of a synthetic high-salinity wastewater (1.0 mg P/L of HEDP), whereas only ∼2 BV of effective treatment capacity was received by PsAX. The exhausted HNdO@PsAX was amenable to a complete regeneration by a binary NaOH NaCl solution without significant loss in capacity. The capability in removing other organic phosphonates and treating a real electroplating wastewater by HNdO@PsAX was further validated. Generally, HNdO@PsAX exhibited a great potential in efficiently removing phosphonates from high-salinity wastewater.

研究领域: 环境科学 · 材料科学
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International Journal of Nanomedicine · 2024 · IF 6.6

Alendronate Functionalized Bone-Targeting Pomolic Acid Liposomes Restore Bone Homeostasis for Osteoporosis Treatment

Demeng Xia,Qingqing Qian,Sheng Wang,Xiao Dong,Ying Liu

Introduction Osteoporosis, characterized by dysregulation of osteoclastic bone resorption and osteoblastic bone formation, severely threatens human health during aging. However, there is still no good therapy for osteoporosis, so this direction requires our continuous attention, and there is an urgent need for new drugs to solve this problem.Methods Traditional Chinese Medicine Salvia divinorum monomer pomolic acid (PA) could effectively inhibit osteoclastogenesis and ovariectomized osteoporosis. However, its poor solubility and lack of targeting severely limits its further application. A novel bone-targeting nanomedicine (PA@TLipo) has been developed to reconstruct the osteoporotic microenvironment by encapsulating pomolic acid in alendronate-functionalized liposomes. Through a series of operations such as synthesis, purification, encapsulation, and labeling, the PA@TLipo have been prepared. Moreover, the cytotoxicity, bone targeting and anti-osteoporosis effect was verified by cell and animal experiments.Results In the aspect of targeting, the PA@TLipo can effectively aggregate on the bone tissue to reduce bone loss, and in terms of toxicity, PA@TLipo could increase the bone target ability in comparison to nontargeted liposome, thereby mitigating systemic cytotoxicity. Moreover, PA@TLipo inhibited osteoclast formation and bone resorption in vitro and reduced bone loss in ovariectomy-induced osteoporotic mice.Conclusion In this study, a novel therapeutic agent was designed and constructed to treat osteoporosis, consisting of a liposome material as the drug pocket, PA as the anti-osteoporosis drug, and ALN as the bone-targeting molecule. And our study is the first to employ a bone-targeted delivery system to deliver PA for OVX-induced bone loss, providing an innovative solution for treating osteoporosis.

研究领域: 药理学 · 骨生物学 · 纳米医学
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2025 · IF 8.5

Alendronate and polyelectrolyte synergically induce biomimetic mineralization of collagen and demineralized dentin

Leiqing Zhang,Zihuai Zhou,Zhiwen Liu,Ying Shi,Yingjie Mao,Baiping Fu,Zhe Wang

Alendronate (ALN), a potent bisphosphonate, plays a significant role in both bone formation and osteoporosis therapy. However, its potential to promote biomimetic mineralization of type I collagen fibrils and demineralized dentin remains unclear. This study reveals that ALN-pretreated collagen fibrils form ester bonds between the hydroxyl groups of ALN and the carboxyl groups of collagen, accompanied by a reduction in collagen surface potential. Additionally, an adsorption equilibrium of ALN to collagen was achieved at 25 mM ALN. ALN pretreatment facilitates intrafibrillar mineralization of type I collagen fibrils in a dose-dependent manner, as well as mineralization of demineralized dentin in synergy with polyelectrolyte-stabilized Amorphous Calcium Phosphate (ACP) nanoparticles. This process effectively restores the mechanical properties of demineralized dentin to levels comparable to natural dentin. Thus, ALN holds potential for localized applications aimed at promoting remineralization of demineralized dentin.

研究领域: 口腔医学 · 材料科学 · 生物医学工程
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JOURNAL OF LABELLED COMPOUNDS & RADIOPHARMACEUTICALS · 2018 ·Vol. 62 ·期 1 ·43-51 · IF 1.423

Radiolabeling, quality control, biodistribution, and imaging studies of 177Lu-ibandronate

Qin Xu,Shumao Zhang,Yan Zhao,Yue Feng,Lin Liu,Liang Cai,Wei Zhang,Zhanwen Huang,Hongyuan Wei,Liangang Zhuo,Yue Chen

The purposes of this study were as follows: (1) to radiolabel ibandronic acid (IBA, a third-generation bisphosphonate) with 177 Lu, investigating optimal labeling conditions, and (2) to analyze biodistribution and imaging properties of intravenous 177 Lu-ibandronate ( 177 Lu-IBA) administered in animals. 177 Lu-labeled methylene diphosphonate ( 177 Lu-MDP) served as a comparator agent. Differing proportions of IBA solution and 177 LuCl 3 solution were combined to determine an optimal ratio for radiolabeling purposes, varying pH, temperature, and time to establish ideal reactivity conditions. Radiochemical purity of the labeled compounds was then assessed by paper chromatography. In vitro and in vivo stabilities were also measured at specific time intervals. In Kunming mice, biodistributions of 177 Lu-IBA and 177 Lu-MDP and respective agent activities in various organs were monitored by gamma counter, and we performed single photon computed tomography/computed tomography (SPECT/CT) imaging of 177 Lu-IBA in normal New Zealand White rabbits. Radiolabeling yields for 177 Lu-IBA proved to be >97% within 30 minutes at 90°C, and its radiochemical purity ensured stability in vitro and in vivo. Furthermore, we found that 177 Lu-IBA is readily soluble in water, showing higher skeletal uptake than 177 Lu-MDP but lower uptake by liver and spleen. The image quality of 177 Lu-IBA was so clear that even after 6 days, analysis was still feasible.

研究领域: 核医学 · 药理学 · 分子影像学
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Acta Biomaterialia · 2017 · IF 6.319

Nanocomposite hydrogels stabilized by self-assembled multivalent bisphosphonate-magnesium nanoparticles mediate sustained release of magnesium ion and promote in-situ bone regeneration

Kunyu Zhang,Sien Lin,Qian Feng,Chaoqun Dong,Yanhua Yang,Gang Li,Liming Bian

Hydrogels are appealing biomaterials for applications in regenerative medicine due to their tunable physical and bioactive properties. Meanwhile, therapeutic metal ions, such as magnesium ion (Mg 2+ ), not only regulate the cellular behaviors but also stimulate local bone formation and healing. However, the effective delivery and tailored release of Mg 2+ remains a challenge, with few reports on hydrogels being used for Mg 2+ delivery. Bisphosphonate exhibits a variety of specific bioactivities and excellent binding affinity to multivalent cations such as Mg 2+ . Herein, we describe a nanocomposite hydrogel based on hyaluronic acid and self-assembled bisphosphonate-magnesium (BP-Mg) nanoparticles . These nanoparticles bearing acrylate groups on the surface not only function as effective multivalent crosslinkers to strengthen the hydrogel network structure, but also promote the mineralization of hydrogels and mediate sustained release of Mg 2+ . The released Mg 2+ ions facilitate stem cell adhesion and spreading on the hydrogel substrates in the absence of cell adhesion ligands, and promote osteogenesis of the seeded hMSCs in vitro . Furthermore, the acellular porous hydrogels alone can support in situ bone regeneration without using exogenous cells and inductive agents, thereby greatly simplifying the approaches of bone regeneration therapy. Statement of Significance In this study, we developed a novel bioactive nanocomposite hydrogel based on hyaluronic acid and self-assembled bisphosphonate-magnesium (BP-Mg) nanoparticles. Such hydrogels are stabilized by the multivalent crosslinking domains formed by the aggregation of Ac-BP-Mg NPs, and therefore show enhanced mechanical properties , improved capacity for mineralization, and controlled release kinetics of Mg 2+ . Moreover, the released Mg 2+ can enhance cell adhesion and spreading, and further promote the osteogenic differentiation of hMSCs. Owing to these unique properties, these acellular hydrogels alone can well facilitate the in vivo bone regeneration at the intended sites. We believe that the strategy reported in this work opens up a new route to develop biopolymer-based nanocomposite hydrogels with enhanced physical and biological functionalities for regenerative medicine.

CAS / MDL: 7791-18-6
研究领域: 生物材料学 · 再生医学 · 骨科
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