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Hf(IV)
Advanced Science · 2025 · IF 14.1

A Hf(IV)-Coordinated NIR-II Fluorescence “Turn-On” Nanoprobe for Precise Imaging-Guided Surgery in Breast Cancer

Yueyang He,Jinyan Lin,Jingwen Bai,Xiao Shen,Kangliang Lou,Yuanyuan Zhu,Zishan Qiao,Weiling Chen,Yang Li,Xiaolong Liu,Guojun Zhang

Breast-conserving surgery (BCS) has become the standard care for early-stage breast cancer. The accurate assessment of tumor margins is urgently required for BCS because positive resection margins often lead to local recurrence. To address this clinical dilemma, a Hf(IV)-coordinated NIR-II fluorescence “turn-on” nanoprobe based on the clinically approved NIR-II fluorescent dye indocyanine green (ICG) for intraoperative tumor visualization is developed. Notably, the fluorescence of ICG can be efficiently quenched by Hf(IV) and subsequently recovered in vivo, showing a remarkable fluorescence “quenching-recovery-amplification” capacity. This nanoprobe can effectively accumulate in tumor sites, accurately identifying submillimeter-sized primary and residual tumors with high sensitivity. In addition, subcutaneous, muscle-infiltrating, and orthotopic breast cancer models are built to repeatedly prove that this ultrasensitive nanoprobe is feasible for precise imaging-guided surgery in breast cancer. Overall, this study constructs an activatable fluorescent nanoprobe for real-time intraoperative tumor margin visualization, holding promise for complete surgical resection and reduction of local recurrence.

研究领域: 肿瘤学 · 生物医学工程 · 分子影像学
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JOURNAL OF MOLECULAR STRUCTURE · 2022 · IF 3.841

Selectivity of novel PAMAM dendrimers modified with salicylaldehyde and their extraction/separation performance on Zr(Ⅳ) and Hf(Ⅳ)

Wei Qin,Xue Han,Junwei Wang,Xie Wang,Jianli Zhang

To design some excellent extractants for the separation of Zr(Ⅳ) and Hf(Ⅳ), a novel set of polyamidoamine dendrimers peripherally modified with salicylaldehyde (Abbreviated as PAMAM-SA) have been synthesized. UV-vis absorption and fluorescent spectrometry were used to study the selectivity of G.1.0, G2.0, G3.0 and G4.0 PAMAM-SA on Zr(Ⅳ) and Hf(Ⅳ) compared with other metal ions, and their extraction/separation performance on Zr(Ⅳ) and Hf(Ⅳ) was also investigated under different pH solutions. The results show that these dendrimers have superior selectivity on Zr(Ⅳ) and Hf(Ⅳ) as compared with Ca 2+ , Mg 2+ , Fe 3+ and Ni 2+ ions. The binding stoichiometry of G1.0, G2.0, G3.0 and G4.0 PAMAM-SA dendrimers with Zr(Ⅳ) is 1:4, 1:8, 1:10, 1:16 molar ratio determined by fluorescent titration respectively and the molar ratio of these dendrimers with hafnium is similar to that of zirconium. Both of the maximum extraction efficiency (EE%) on Zr(Ⅳ) and the separation coefficient (β Zr/Hf ) are following the order of G2.0-PAMAM-SA > G1.0-PAMAM-SA > G3.0-PAMAM-SA > G4.0-PAMAM-SA, and the maximum EE% on Zr(Ⅳ) is up to 98.9% and furthermore the β Zr/Hf is 1.52 for G2.0-PAMAM-SA at lower acid concentration compared with the reported extractants. The favorable higher EE% and β Zr/Hf indicate that G2.0-PAMAM-SA may be potentially employed as a highly selective and efficient extractant to enhance separating zirconium from hafnium.

CAS / MDL: 7782-61-8 13478-00-7
研究领域: 化学 · 材料科学
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RSC Advances · 2021 ·Vol. 11 ·期 55 ·34754-34765 · IF 3.361

Phosphorous-functionalized PAMAM dendrimers supported on mesoporous silica for Zr(IV) and Hf(IV) separation

Wei Qin,Kaixuan Xu,Junwei Wang,Xiaofeng Cui,Jianli Zhang,Yaqing Weng

To overcome the urgency of zirconium and hafnium separation, a novel mesoporous silica sorbent (PS-G1.0-MSNs) modified with phosphorous-functionalized G1.0 PAMAM dendrimers was prepared. The adsorption and separation behaviors of PS-G1.0-MSNs adsorbent on Zr(IV) and Hf(IV) were perfromed as a function of acidity, contact time, temperature, and ion concentrations by batch sorption methods. The maximum adsorption capacities for Zr(IV) and Hf(IV) were 25.7 mg g−1 and 5.36 mg g−1 under optimal experimental conditions, respectively, and the separation factor βHf/Zr = 2.0 > 1 demonstrated that the prepared sorbent had preferential selectivity for Hf(IV) in rich Zr(IV) solution. Moreover, kinetic data indicated that the sorption process on Zr(IV) and Hf(IV) achieved equilibrium within 120 min, and followed the pseudo-first-order model with a rate-determining step. The adsorption amount increased as temperature raised from 283 K to 303 K and the isothermal data plotted with the Langmuir model was better than the Freundlich model with monolayer behavior. Thermodynamic data analysis indicated that the sorption process was spontaneous and endothermic. Furthermore, XPS analysis revealed that the metal ion adsorption was mainly induced by the chemical coordination of Zr(IV) and Hf(IV) ions with N, O, P atoms of amide and phosphate groups. The present work provides good guidelines on the design of high efficient sorbent for the separation of Hf(IV) from Zr(IV) solutions.

研究领域: 材料科学 · 化学工程 · 环境科学
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JOURNAL OF RADIOANALYTICAL AND NUCLEAR CHEMISTRY · 2026 · IF 1.7

Separation of Hf(IV) and Zr(IV) using di(p-tert-octylphenyl) phosphate in sulfuric acid medium

Liu Xiaotong,Li Hui,Xu Chengjin,Peng Xiujing,Sun Guoxin,Cui Yu,Lu Ping

Efficient separation of nuclear-grade zirconium (Zr) and hafnium (Hf) remains a significant challenge in the nuclear industry. In this study, a novel extractant, di(p-tert-octylphenyl) phosphate (DTOPPA), was designed and synthesized. DTOPPA demonstrated preferential extraction of Hf over Zr in sulfuric acid media, surpassing the performance of conventional extractants such as D2EHPA and PC88A. Under optimized conditions, Hf(IV) extraction achieved 90.7% with a separation factor SF (Hf/Zr) of 13.4. Density functional theory (DFT) calculations and acid–base titration indicated enhanced dissociation of DTOPPA, attributed to the electron-withdrawing phenoxy group, which facilitates cation exchange. Slope analysis, saturation capacity measurements, and Fourier-transform infrared spectroscopy (FTIR) identified the extracted species as Zr(Hf)OA 2 ·2DTOPPA, involving cation exchange and P=O coordination. Selective stripping of Zr was accomplished using dilute sulfuric acid, while oxalic acid efficiently stripped Hf. A two-stage countercurrent extraction process yielded nuclear-grade Zr with stable organic phase recycling. This novel extractant provides an environmentally friendly and efficient method for Zr/Hf separation with significant potential for industrial application.

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