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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Surface-complexation-directed selective oxidation of phosphonates by decoration of copper anchoring sites

Hao Wang,Zixuan Zeng,Ran Duan,Hua Sheng,Chao Shan,Wenjing Song,Jincai Zhao

Organic phosphonates are recalcitrant contaminants in industrial and municipal wastewater. Their oxidative conversion to phosphate is promising for the in-depth removal and recovery of phosphorus. However, the treatment by conventional advanced oxidation processes (AOPs) usually demonstrates no precedence toward phosphonates, suffering from severe interference from co-existing substances and the overuse of costly oxidants. Herein we develop a copper-directed protocol for highly selective oxidation of phosphonates driven by simulated solar irradiation. Exploiting copper nanostructures decorated bismuth vanadate, hydroxyethylidene diphosphonic acid (HEDP), a representative phosphonate, converted to phosphate at > 93  % yield in two hours. Distinguished from Fe/UV or copper-free light-driven oxidation that is susceptible to common anions/organic matters, the protocol developed here offered excellent anti-interference performance, and was applicable for oxidative removal of HEDP in actual water matrices, maintaining 70–80 % yield of phosphate. Copper-promoted oxidation was also demonstrated for PBTC (2-phosphonobutane-1,2,4-tricarboxylic acid), EDTMP (ethylenediamine tetra (methylene phosphonic acid)) and DTPMP (diethylenetriamine penta (methylene phosphonic acid)). Other than free radical mediated process, the copper enhanced phosphonate-catalyst interaction enables directional interfacial hole transfer to phosphonates, triggering their conversion to phosphate. The revealed selective oxidation pathway is envisioned to guide new protocol design for advanced treatment of phosphorus-containing wastewater.

研究领域: 环境科学 · 化学
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JOURNAL OF HAZARDOUS MATERIALS · 2023 · IF 13.6

Highly efficient removal of phosphonates by ferrate-induced oxidation coupled with in situ coagulation

Wen-Yuan Fan,Xin Zhang,Pu-Can Guo,Guo-Ping Sheng

Phosphonates, as a kind of important organic phosphorus in wastewater, should be removed in terms of their environmental risks. Unfortunately, traditional biological treatments fail to remove phosphonates effectively due to their biological inertness. The reported advanced oxidation processes (AOPs) usually require pH adjustment or coupling with other technologies to achieve high removal efficiency. Thus, a simple and efficient method for phosphonate removal is urgently needed. Herein, ferrate was found to remove phosphonates effectively in one-step under near-neutral circumstances by coupling oxidation and in-situ coagulation. Nitrilotrimethyl-phosphonic acid (NTMP), a typical phosphonate, could be efficiently oxidized by ferrate to release phosphate. The fraction of phosphate release increased with increasing ferrate dosage and reached 43.1% when 0.15 mM ferrate was added. Fe(VI) was responsible for NTMP oxidation, while Fe(V), Fe(IV) and ⋅OH played a minor role. Ferrate-induced phosphate release facilitated total phosphorus (TP) removal, because the phosphate is more easily removed via ferrate-resultant Fe(III) coagulation than the phosphonates. The coagulation removal of TP could reach up to 90% within 10 min. Furthermore, ferrate exerted high removal efficiencies for other commonly used phosphonates with approximately or up to 90% TP removal. This work provides a one-step efficient method to treat phosphonate-containing wastewaters.

研究领域: 环境科学 · 水处理技术
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JOURNAL OF APPLIED POLYMER SCIENCE · 2019 ·Vol. 136 ·期 25 ·47593 · IF 2.188

Fire retardance and smoke suppression of polypropylene with a macromolecular intumescent flame retardant containing caged bicyclic phosphate and piperazine

Rong Yang,Binbin Ma,Xin Zhang,Jinchun Li

A macromolecular intumescent flame retardant (FR) named PPPAP was designed and synthesized with phosphorus chloride (the acid source), 2,6,7-trioxa- l -phosphabicyclo[2.2.2]-octane-4-methanol (the charring agent), and anhydrous piperazine (the blowing agent). Then, it was used to prepare an intumescent flame-retardant polypropylene (FR-PP). The thermal stability, flame retardancy, and fire performance of the FR-PPs were investigated. The results show that the initial decomposition temperature and char residue at 700 °C of PPPAP were 260.8 °C and 31.8%, respectively. The limiting oxygen index (LOI) value of polypropylene (PP) was enhanced with increasing PPPAP content. With the addition of 40 wt % PPPAP, the LOI value of FR-PP was 29%, and it passed the vertical burning UL-94 V-0 rating. The cone calorimetry results indicate that not only the peak heat-release rate but also the total smoke production of PP significantly decreased to 65.7 and 79.5%, respectively, with the incorporation of only 20 wt % PPPAP. The FR mechanism suggested that PPPAP played a part in both the gas and condensed phases, and the formation of the intumescent char layer during combustion was the dominant FR mechanism. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136 , 47593.

研究领域: 材料科学 · 高分子化学
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JOURNAL OF APPLIED POLYMER SCIENCE · 2023 ·Vol. 140 ·期 41 ·e54513 · IF 3

A nitrogen-rich DOPO-based phosphoramide for improving the fire resistance of polycarbonate with comparable mechanical property

Boyu Cai,Qing Jiang,Wendi Xu,Luze Wang,Zhonglin Luo,Biaobing Wang

A nitrogen-rich DOPO-based phosphoramide (DPAPZ) was synthesized using aminopyrazine and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) as raw materials, and blended with polycarbonate (PC) through melting method. The chemical structure of DPAPZ was validated by FTIR, 1 H NMR and 31 P NMR. The presence of DPAPZ endowed PC/DPAPZ composites with better fire safety and smoke suppression. With the incorporation of 6 wt% DPAPZ, PC/DPAPZ-6 composite reached UL-94 V-0 rating and 30.2% of limiting oxygen index value. Simultaneously, the peak of heat release rate and total heat release of PC/DPAPZ-6 were reduced by 44.8% and 47.0% as compared with the pure PC, respectively. The DPAPZ displayed bi-phase flame retardant roles. In the gas phase, the decomposition of DPAPZ released phosphorus-containing free radicals acting as the quencher of reactive H·/OH· and nonflammable NH 3 diluting O 2 /combustible volatiles. In the condensed phase, the phosphorus-containing components were dehydrated into metaphosphoric acid or polymetaphosphate covering the surface to protect the PC matrix from further combustion, and to promote the formation of a dense carbon layer to interrupt the transmission of O 2 and volatiles between the combustion zone and the inner. The tensile strength of the composites displayed almost no change but the elongation at break decreased slightly with the addition of DPAPZ.

CAS / MDL: 5049-61-6 35948-25-5
研究领域: 材料科学 · 化学工程
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2024 · IF 7.7

How the chemical structure of phosphoramides affect the fire retardancy and mechanical properties of polylactide?

Yijiao Xue,Tianchen Zhang,Linfeng Tian,Jiabing Feng,Fei Song,Zheng Pan,Guobo Huang,Meng Zhang,Yonghong Zhou,Pingan Song

Phosphoramides, as a kind of high-efficient fire retardants, have been designed in many structures and endowed exceptional fire retardancy to polylactide (PLA). However, due to ignorance of the structure-property correlation, the effect of phosphoramides' structure on the fire retardancy and mechanical properties of PLA is still unclear. Herein, a series of biobased phosphoramides (phosphoramide (V1), linear polyphosphoramide (V2) and hyperbranched polyphosphamide (V3)) were designed and incorporated into PLA, and the structural effect of phosphoramides on the fire-retardant and mechanical properties of PLA was deeply researched. Among three kinds of phosphoramides, the hyperbranched polyphosphoramide is more effective than the corresponding linear polyphosphoramide and phosphoramide in improving the fire-retardant and anti-dripping properties of PLA, and only linear polyphosphoramide shows a positive effect in the mechanical strength of PLA. This work provides a feasible strategy for creating mechanically robust and fire-retardant polymer composites by molecularly tailoring the structure of fire retardants and uncovering their structure-property relationship.

CAS / MDL: 109-99-9
研究领域: 材料科学 · 化学工程
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COMPOSITES PART A-APPLIED SCIENCE AND MANUFACTURING · 2022 · IF 9.463

A polyphosphoramide-grafted lignin enabled thermostable and fire-retardant polylactide with preserved mechanical properties

Lina Liu,Bingbing Shi,Anlin Zhang,Yijiao Xue,Jianzhong Zhang,Jinfeng Dai,Morteza Hassanpour,Long-Cheng Tang,Yongqian Shi,Pingan Song

It has been desirable to create biodegradable polymer materials that are thermally stable, flame- retardant and mechanically robust. One promising strategy is to develop fire retardant polylactide (PLA) using lignin as inexpensive fillers, but existing functionalized lignin cannot improve the thermal stability of PLA, in addition to unsatisfactory fire retardancy. Herein, we report a lignin-derived fire retardant (LF) by grafting polyphosphoramide into the chemical structure of lignin waste through graft polymerization. The results show that with 8 wt% of LF, the final PLA shows significantly enhanced thermal stability in N 2 . Moreover, the resulting PLA achieves a satisfactory UL-94 V-0 rating, meeting the demanding requirement of fire retardancy in industries. Additionally, the PLA/LF composite displays increased elastic modulus and well-preserved strength and ductility of pure PLA. This work provides an effective strategy for creating biobased fire retardant additives using industrial lignin waste, and PLA biocomposites which hold great promise for packaging, fabrics, electronic, and automotive applications.

研究领域: 材料科学 · 生物质工程
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Frontiers in Neuroscience · 2021 · IF 4.677

Low-Dose Cyclophosphamide Induces Nerve Injury and Functional Overactivity in the Urinary Bladder of Rats

Wang Rui,Hong Ming,Huang Jingyi,Zhou Na,Zhang Yao,Xu Siyuan,Liu Jiaye,Yuan Junjie,Zhang Lusiqi,Huang Linyuan,Huang Ping,Tan Bo,Cao Hong-ying

Aim: This research aimed to investigate the neurotoxicity of low-dose cyclophosphamide (CYP) on the urinary bladder of rats by in vivo and in vitro studies.Methods: To establish CYP-induced cystitis rat model, rats were treated with three intraperitoneal injections of CYP (25 mg/kg) in a week. During treatment, the up-down method was used to assess the mechanical withdrawal threshold. On day 8, urodynamic test and bladder smooth muscle contractility study, including the contraction of bladder strips to electrical field stimulation (EFS, 2–64 Hz), carbachol (CCh, 10–8–10–5 M) and KCl (120 mM), were performed to evaluate the function of bladder function. Body weight and bladder weight were also recorded. Morphometric analysis using an optical microscope and transmission electron microscope was performed to observe the changes of microstructure and submicrostructure of the bladder. The major pelvic neurons were isolated and treated with acrolein (the main CYP metabolite) to assess apoptosis in vitro. RT-PCR assays were used to quantify the mRNA expression levels of Nlrp6, Asc, Casp11 and Casp1 in bladder tissues and primary neurons.Results: After CYP injections, the body weights decreased, but the bladder weights increased in the model group. The mechanical withdrawal threshold of the cystitis model remained at a low level. The morphometric analysis suggested bladder inflammation and neuroinflammation in the bladder of the cystitis rat model. Urodynamic test revealed that, the amplitude, the pressure baseline, the peak pressure and pressure threshold of model rats significantly increased after CYP treatment. The muscle strips of model rats exhibited significantly higher contractility caused by EFS and CCh than the controls. Apoptotic cells appeared at the highest concentration group (100 μM acrolein) after 6 h of acrolein incubation in apoptosis assay of primary neurons. The mRNA expression levels of Nlrp6 and Casp11 were significantly increased in the cystitis rat model and in the acrolein-treated neurons.Conclusions: Low-dose CYP treatment was confirmed to induce nerve injury, which leading to bladder pain and overactive bladder in female rats, and the up-regulation of Nlrp6 and Casp11 may contribute to these pathological changes.

研究领域: 药理学 · 神经科学 · 泌尿学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2025 · IF 9

New insight to phosphonate degradation by electrochlorination: Hypochlorous acid dominated dephosphorylation through selective attacking CP bond

Wubin Liao,Peng Liao,Zheng Wang,Chenggang Ci,Shiwei Xie

The dephosphorylation of N-containing phosphonates is crucial for mitigating their potential ecological risks and enabling phosphorus resource recovery. Here, we first show that the electrochlorination process outperforms other advanced oxidation methods in terms of conversion efficiency and rate constants for orthophosphate production. The high efficacy of electrochlorination process is primarily attributed to the generation of hypochlorous acid (HClO) under neutral pH conditions, as substantiated by a combination of speciation analysis, quantitative assessments, and quenching experiments. Furthermore, density functional theory (DFT) calculation and LC-MS measurements show that the degradation of nitrilotris-methylenephosphonic acid (NTMP) by HClO occurs spontaneously, with a preferential cleavage of the C P bond over the C N bond, thereby facilitating the efficiency of the dephosphorylation reaction. Altogether, our findings provide key insights into the role of reactive chlorine species in the degradation of N-containing phosphonates, offering valuable evidence for the development of next-generation, more effective phosphorus recovery strategies.

研究领域: 环境科学 · 化学工程 · 计算化学
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Biosensors-Basel · 2023 ·Vol. 13 ·期 5 ·560 · IF 5.4

Graphene-Based Metamaterial Sensor for Pesticide Trace Detection

Tingting Lang,Meiyu Xiao,Wenyang Cen

Organophosphate insecticides with broad spectrum and high efficiency make a great difference to agricultural production. The correct utilization and residue of pesticides have always been important issues of concern, and residual pesticides can accumulate and pass through the environment and food cycle, resulting in safety and health hazards to humans and animals. In particular, current detection methods are often characterized by complex operations or low sensitivity. Fortunately, using monolayer graphene as the sensing interface, the designed graphene-based metamaterial biosensor working in the 0–1 THz frequency range can achieve highly sensitive detection characterized by spectral amplitude changes. Meanwhile, the proposed biosensor has the advantages of easy operation, low cost, and quick detection. Taking phosalone as an example, its molecules can move the Fermi level of graphene with π–π stacking, and the lowest concentration of detection in this experiment is 0.01 μg/mL. This metamaterial biosensor has great potential in detecting trace pesticides, and its application in food hygiene and medicine can provide better detection services.

CAS / MDL: 2310-17-0
研究领域: 食品科学 · 生物医学工程
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Antioxidants · 2020 ·Vol. 9 ·期 8 ·745 · IF 5.014

Protective Effect of Low Molecular Weight Peptides from Solenocera crassicornis Head against Cyclophosphamide-Induced Nephrotoxicity in Mice via the Keap1/Nrf2 Pathway

Shuoqi Jiang,Zhuangwei Zhang,FangFang Huang,Zuisu Yang,Fangmiao Yu,Yunping Tang,Guofang Ding

The major component of theSolenocera crassicornishead protein hydrolysates-fraction 1 (SCHPs-F1) are low molecular weight peptides (MW < 1 kDa). In this study, we investigated the potential renoprotective effects of SCHPs-F1 in a cyclophosphamide (CTX) toxicity mouse model. In brief, 40 male mice were randomly divided into 5 groups and received either saline or 80 mg/kg body weight (BW) CTX by intraperitoneal injection for 5 days, followed by either saline or SCHPs-F1 (100, 200, and 400 mg/kg BW) by intragastric administration for 15 days. SCHPs-F1 treatment significantly reversed the CTX-induced decreases in the levels of blood urea nitrogen (BUN), creatinine (CRE), and cytochrome P450 (CYP450), as well as the renal histological lesions. Furthermore, the results indicated that SCHPs-F1 potentially alleviated CTX-induced nephrotoxicity through mitigating inflammatory responses, oxidative stress, and apoptosis status of the kidneys, as evidenced by decreased levels of malondialdehyde (MDA), interleukin (IL)-1β, IL-6, tumor necrosis factor (TNF)-α, and interferon (IFN)-γ and increased levels of total antioxidant capacity (T-AOC), catalase (CAT), superoxide dismutase (SOD) and glutathione peroxidase (GSH-Px). Moreover, overexpression of pro-apoptotic proteins pair B-cell lymphoma-2 (Bcl-2)-associated X (Bax)/Bcl-2, cysteinyl aspartate specific proteinase (caspase)-3 and caspase-9 in renal tissues were suppressed by treatment with SCHPs-F1. In addition, the protein levels of the antioxidant factor nuclear factor erythroid-2 related factor 2 (Nrf2) and the expression levels of its downstream target genes heme-oxygenase (HO-1), glutamate-cysteine ligase modifier subunit (GCLM) and NAD(P)H dehydrogenase (quinone) 1 (NQO-1) were stimulated by treatment with SCHPs-F1 in the CTX-induced renal injury model. Taken together, our data suggested that SCHPs-F1 could provide a novel potential strategy in mitigating the nephrotoxicity caused by CTX.Keywords:apoptosis;cyclophosphamide;inflammation;oxidative stress;peptides;Solenocera crassicornis

研究领域: 药理学 · 毒理学 · 分子生物学
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REPRODUCTIVE TOXICOLOGY · 2025 · IF 2.8

Protocatechualdehyde improves cyclophosphamide-induced premature ovarian insufficiency by inhibiting granulosa cell apoptosis and senescence through the SIRT1/p53 axis

Cong Feng,Yue Jiang,Yi Wang,Yuehui Zhang,Yu Liu,Jia Li

Premature ovarian insufficiency (POI) is a prevalent gynecological disorder. Cyclophosphamide (CP), as a chemotherapeutic drug, particularly plays an important role in inducing POI. Protocatechualdehyde (PCA) is a major phenolic acid in Chinese herb Danshen, and has been reported to have beneficial effects on anti-inflammatory, anti-apoptotic, and anti-oxidant functions. We aimed to investigate the effect of different doses of PCA on ovarian function and the underlying molecular mechanisms. PCA administration reduced estrous cycle disorders, increased ovarian weight, promoted the secretion of serum hormone levels, and improved the CP-damaged ovarian microenvironment. Importantly, the administration of PCA contributed to the recovery of ovarian function with POI by inhibiting the senescence and apoptosis of granulosa cells. In vitro assay further confirmed the protective effect of PCA on CP-induced senescence and apoptosis of granulosa cells. Mechanistically, both in vivo and in vitro experiments proved that PCA administration promoted activation of the Sirt1/p53 signaling cascade, ultimately improving ovarian function. In conclusion, PCA might protect against ovarian damage in CP-induced POI that might be related to its activity on senescence and apoptosis of granulosa cells by the Sirt1/p53 pathway.

CAS / MDL: 28718-90-3
研究领域: 生殖医学 · 药理学 · 分子生物学
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ECOTOXICOLOGY AND ENVIRONMENTAL SAFETY · 2021 · IF 6.291

Cyclophosphamide induced physiological and biochemical changes in mice with an emphasis on sensitivity analysis

Zhiying Zhang,Ting Pan,Chunrong Liu,Xiaoyun Shan,Zeqiong Xu,Huachang Hong,Hongjun Lin,Jianrong Chen,Hongjie Sun

The widespread use of cyclophosphamide (CP) in medical treatment had caused ubiquitous contamination in the environment. To data, many studies have been carried out on the toxic effect of CP. However, among these toxic effects of CP, which are the most sensitive remains unclear. Present study aimed to investigate the toxicity of CP on mice and evaluate the sensitivity of physiological-biochemical parameters upon exposure of mice to CP. Results showed that as compared with the control group, CP caused significant reduction in body weight (p < 0.01), spleen coefficient (p < 0.01), leukocyte density (p < 0.01) and alanine transaminase (ALT) in kidney (p < 0.01); However superoxide dismutase (SOD), malondialdehyde (MDA), ALT in liver and creatinine (Cr) in kidney significantly (p < 0.05) increased. Among the suppressed physiological and biochemical parameters, the sensitivity to CP toxicity was generally ranked as body weight > leukocyte density > ALT in kidney > spleen coefficient; while among the stimulated parameters, the sensitivity was ranked as MDA (liver) > Cr (kidney) > ALT (liver). Overall, the most sensitive parameters to CP toxicity may be associated with growth, immune system and the normal function of liver and kidney.

研究领域: 毒理学 · 生物化学 · 环境科学
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