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TALANTA · 2015 · IF 3.545

Development of Hf4+-immobilized polydopamine-coated magnetic graphene for highly selective enrichment of phosphopeptides

Haizhu Lin,Chunhui Deng

In this work, we first designed and synthesized an IMAC material with Hf 4+ immobilized on polydopamine-coated magnetic graphene and applied it to phosphopeptides enrichment successfully. The newly prepared material gathered the advantages of large specific surface area of graphene, good hydrophilicity and biocompatibility of polydopamine and superparamagnetism of Fe 3 O 4 . We investigated the performance of Hf 4+ -immobilized polydopamine-coated magnetic graphene (denoted as magG@PDA-Hf 4+ ) in phosphopeptides enrichment and the results showed high selectivity and sensitivity of the new material. Finally, we successfully applied magG@PDA-Hf 4+ to phosphopeptides enrichment from non-fat milk digests and human serum, further demonstrating excellent performance of this new material in phosphopeptides enrichment.

研究领域: 生物化学 · 分析化学
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NEW JOURNAL OF CHEMISTRY · 2024 ·Vol. 48 ·期 17 ·7718-7725 · IF 2.7

Novel phosphate ester extractant for preferential extraction of hafnium over zirconium and its mechanism

Yanping Luo,Chengjin Xu,Jianhui Su,Xiujing Peng,Xiangfeng Kong,Shuo Wang,Jiahui Sun,Yu Cui,Yong Nie,Xuchuan Jiang,Guoxin Sun

Nuclear-grade zirconium and hafnium play an essential role in the nuclear industry. It is difficult to separate and purify zirconium and hafnium because of the similar properties caused by lanthanide shrinkage and the preferential extraction of hafnium is challenging. In this work, a new extractant, di(p-tert-butylphenyl)phosphate (DTBPPA), was synthesized, and its separation performance of zirconium and hafnium in the sulfuric acid system was evaluated. Under identical extraction conditions, DTBPPA shows excellent preferential extraction properties for hafnium compared to current commercial extractants, such as D2EHPA and PC88A. The highest SFHf/Zr value is up to 16.3. A crystal of the hafnium extracted species was grown to study the extraction mechanism and the principle of preferential extraction of hafnium. It was found that the crystal growth of zirconium-extracted species was difficult under the same conditions. Hafnium extracted species crystals reveal a six-coordinated hafnium ion bound to six extractant molecules. The electron withdrawing effect of the aromatic substituents results in a low electron density of O atoms in the P–O group of the new extractant, and the extractant coordination group shows the characteristics of a soft base. This matches the soft acid properties of hafnium ions. DTBPPA shows a solid ability to identify hafnium ions, thus achieving preferential separation of hafnium from zirconium and hafnium mixtures.

CAS / MDL: 10025-87-3
研究领域: 核化学 · 无机化学
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JOURNAL OF MEMBRANE SCIENCE · 2022 · IF 10.53

Highly efficient separation and enrichment of hafnium from zirconium oxychloride solutions by advanced ion-imprinted membrane separation technology

Tingting Tang,Fan Yang,Meiying Xie,Liyan Xue,Zhengming Jiang,Zexing Xie,Kaixian Wang,ZhiWan Li,Laiyao Geng,Tianxi Hu

Hafnium (Hf) is an important strategic material for the semiconductor, aerospace and nuclear industries. In this paper, an advanced ion-imprinted membranes (IIMs) separation system was prepared for the first time to achieve efficient separation and enrichment of Hf ions from zirconium oxychloride solutions. IIMs were constructed by a keyhole complex imprinting method with N , N -di-2-ethylhexyl diglycolamic acid (D2EHDGAA) as the carrier molecule, cellulose triacetate (CTA) as the base polymer and Hf ions as the template ion. In addition, amide acid driven IIMs were coupled with aspartic acid in the feed phase, which changes from preferential extraction of Zr to preferential extraction of Hf. To characterize it, we used Fourier transform infrared (FT-IR) spectroscopy and scanning election microscopy (SEM). The results showed that IIMs can increase C Hf /C Zr from 2.33:100 to 33.33:100 within 1 h compared with polymer inclusion membranes (PIMs) and ionic liquid supported liquid membranes (SLMs), which increased by 3.33 and 3.67 times. The selectivity and enrichment performance for the enrichment of Hf ions from Zr solution were significantly improved due to the high recognition selectivity of ion imprinting. Therefore, IIMs, as an advanced membrane separation system, may have good potential for industrial application in the field of efficient separation and enrichment of Hf ions.

研究领域: 材料科学 · 化学工程 · 核工业技术
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CERAMICS INTERNATIONAL · 2024 · IF 5.1

Effects of Zr4+ and Hf4+ substitution on the structure and dielectric response of Ba4Sm9.33Ti18O54 ceramics

Weijia Guo,Yiming Yang,Zhiyu Ma,Yutian Lu,Zhenxing Yue

Microwave dielectric ceramics with high relative permittivity ( ε r ) are commonly used for the miniaturation of microwave devices. The dielectric loss mechanism of microwave dielectric ceramics , as well as the property modification, has been a concerned topic among scholars. Herein, the lattice structure, defects, and broadband dielectric response of Zr 4+ and Hf 4+ substituted Ba 4 Sm 9.33 Ti 18 O 54 (BST) ceramics are systematically examined. The negative temperature coefficient of resonant frequency ( τ f ) of BST ceramics can be tuned to near zero via ion substitution, owing to the Sm 2 Ti 2 O 7 second phase with a large positive τ f . Optimal microwave dielectric properties of ε r  = 81.3, Q  ×  f  = 10,800 GHz, and τ f  = −4.6 ppm/°C are achieved. The lattice vibration behavior and defect concentration are analyzed by Raman spectra and thermally stimulated depolarization currents (TSDC), respectively. The increasing volume of the unit cell and TiO 6 octahedra, which is because of the large-radius substitution ions, leads to an increase in lattice vibration damping factor and the generation of more oxygen vacancies ( V O ∙ ∙ VO∙∙ ). Therefore, the dielectric losses in the microwave and terahertz (THz) bands increase after substitution. Meanwhile, the low-frequency dielectric losses at high temperatures also increase due to the weak restraint of carriers by the lattice. The broadband loss mechanism of Zr 4+ and Hf 4+ substituted BST ceramics related to lattice vibration and defects might be referenced for developing low-loss dielectric ceramics.

研究领域: 材料科学 · 物理学
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ACS Nano · 2023 · IF 17.1

Nanointegrative In Situ Reprogramming of Tumor-Intrinsic Lipid Droplet Biogenesis for Low-Dose Radiation-Activated Ferroptosis Immunotherapy

Qiqi Zhang,Xuan Wang,Yuanyuan Zhao,Zhuo Cheng,De Fang,Yingqi Liu,Gan Tian,Menghuan Li,Zhong Luo

Low-dose radiotherapy (LDR) has shown significant implications for inflaming the immunosuppressive tumor microenvironment (TME). Surprisingly, we identify that FABP-dependent lipid droplet biogenesis in tumor cells is a key determinant of LDR-evoked cytotoxic and immunostimulatory effects and developed a nanointegrated strategy to promote the antitumor efficacy of LDR through cooperative ferroptosis immunotherapy. Specifically, TCPP-TK-PEG-PAMAM-FA, a nanoscale multicomponent functional polymer with self-assembly capability, was synthesized for cooperatively entrapping hafnium ions (Hf4+) and HIF-1α-inhibiting siRNAs (siHIF-1α). The TCPP@Hf-TK-PEG-PAMAM-FA@siHIF-1α nanoassemblies are specifically taken in by folate receptor-overexpressing tumor cells and activated by the elevated cellular ROS stress. siHIF-1α could readily inhibit the FABP3/7 expression in tumor cells via HIF-1α-FABP3/7 signaling and abolish lipid droplet biogenesis for enhancing the peroxidation susceptibility of membrane lipids, which synergizes with the elevated ROS stress in the context of Hf4+-enhanced radiation exposure and evokes pronounced ferroptotic damage in vital membrane structures. Interestingly, TCPP@Hf-TK-PEG-PAMAM-FA@siHIF-1α-enhanced ferroptotic biomembrane damage also facilitates the exposure of tumor-associated antigens (TAAs) to promote post-LDR immunotherapeutic effects, leading to robust tumor regression in vivo. This study offers a nanointegrative approach to boost the antitumor effects of LDR through the utilization of tumor-intrinsic lipid metabolism.

研究领域: 肿瘤学 · 放射肿瘤学 · 纳米技术 · 免疫疗法 · 分子生物学
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