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RSC Advances · 2023 ·Vol. 13 ·期 16 ·11215-11224 · IF 3.9

Aptamer modified Zr-based porphyrinic nanoscale metal–organic frameworks for active-targeted chemo-photodynamic therapy of tumors

Haidi Feng,Lu Zhao,Zhiqiang Bai,Zhihui Xin,Chaoyu Wang,Lizhen Liu,Jinping Song,Haifei Zhang,Yunfeng Bai,Feng Feng

Active-targeted nanoplatforms could specifically target tumors compared to normal cells, making them a promising therapeutic agent. The aptamer is a kind of short DNA or RNA sequence that can specifically bind to target molecules, and could be widely used as the active targeting agents of nanoplatforms to achieve active-targeted therapy of tumors. Herein, an aptamer modified nanoplatform DOX@PCN@Apt-M was designed for active-targeted chemo-photodynamic therapy of tumors. Zr-based porphyrinic nanoscale metal organic framework PCN-224 was synthesized through a one-pot reaction, which could produce cytotoxic 1O2 for efficient treatment of tumor cells. To improve the therapeutic effect of the tumor, the anticancer drug doxorubicin (DOX) was loaded into PCN-224 to form DOX@PCN-224 for tumor combination therapy. Active-targeted combination therapy achieved by modifying the MUC1 aptamer (Apt-M) onto DOX@PCN-224 surface can not only further reduce the dosage of therapeutic agents, but also reduce their toxic and side effects on normal tissues. In vitro, experimental results indicated that DOX@PCN@Apt-M exhibited enhanced combined therapeutic effect and active targeting efficiency under 808 nm laser irradiation for MCF-7 tumor cells. Based on PCN-224 nanocarriers and aptamer MUC1, this work provides a novel strategy for precisely targeting MCF-7 tumor cells.

CAS / MDL: 65-85-0 13520-92-8
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FOOD CHEMISTRY · 2023 · IF 8.8

Smartphone-assisted ratiometric sensing platform for on-site tetracycline determination based on europium functionalized luminescent Zr-MOF

Yijian Zhao,Meiyi Liu,Shuai Zhou,Zhiyu Yan,Jingsheng Tian,Qiaojuan Zhang,Zhiyi Yao

Accurate on-site analysis of tetracycline (TC) is of great research value for ensuring food safety and estimating environmental pollution. Herein, a smartphone-based fluorescent platform for TC detectionhas been developed based on a europium functionalized metal–organic framework (Zr-MOF/Cit-Eu). Based on the inner filter and antenna effect between Zr-MOF/Cit-Eu and TC, the probe exhibited a ratiometric fluorescent response toward TC, resulting in an emission color change from blue to red. Excellent sensing performance was achieved with a detection limit of 3.9 nM, consistent with the linear operation spanning nearly four orders of magnitude. Subsequently, visual test strips based on Zr-MOF/Cit-Eu were prepared, possessing the potential for accurate testing of TC via RGB signals. Finally, the proposed platform was well applied in actual samples with satisfied recoveries (92.27 to 110.22%). This MOF-based on-site fluorescent platform holds great potential on constructing intelligent platform for visual and quantitative detection of organic contaminants.

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International Journal of Electrochemical Science · 2023 · IF 1.5

High sensitive label-free electrochemical sensor using polydopamine-coated Zr-MOF composites for rapid detection of amoxicillin

Ying Wang,Liya Zhang

In recent years, with the misuse and uncontrolled release of antibiotics, the detection of antibiotics has become an important area of research in analytical chemistry. This work utilizes the self-polymerization property of dopamine in alkaline solution to synthesize polydopamine-coated Zr-MOF composites (Zr-MOF-PDA) using zirconium-based metal-organic framework (Zr-MOF) of ligand 4-carboxyphenylporphyrin as the carrier material. The electrochemical sensor for highly sensitive detection of amoxicillin (AMO) was successfully constructed by drop coating this compliant material on the surface of glassy carbon electrode. The AMO was detected by differential pulse voltammetry under the optimized experimental conditions. The linearity range was 0.25~90 μM, and the detection limit was 71 nM. The sensor was successfully used to determine AMO in river water and tap water samples with good recovery. The proposed sensor provides a feasible solution for the sensitive detection of AMO.

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SENSORS AND ACTUATORS B-CHEMICAL · 2023 · IF 8.4

Cu2+-functionalized Zr-MOF triggers O-phenylendiamine oxidation for ultrasensitive ratiometric fluorescence detection of nerve agent simulant

You Lei,Yuting Gao,Yi Xiao,Pengcheng Huang,Fang-Ying Wu

Developing a fluorescence sensor capable of precisely identifying highly toxic nerve agents has become a focus of research, given that they are easily available and can be used by terrorists to threaten the security of the world. In this work, we designed a ratiometric fluorescence sensing platform with Cu 2+ -modified UiO-66-NH 2 (Cu 2+ @UiO-66-NH 2 ) and o-phenenediamine (OPD) as signal indicators and successfully used for the liquid and gas detection of the nerve agent simulant diethyl chlorophosphate (DCP). UiO-66-NH 2 obtained oxidase activity by simple Cu 2+ modification, which catalyzed the oxidation of OPD to give a yellow fluorescent product 2, 3-diaminophenazine (DAP). In this detection system, the fluorescence of UiO-66-NH 2 was greatly enhanced by blocking the ligand metal charge transfer (LMCT) process inside the framework by DCP. At the same time, the amino group of DAP was phosphorylated by DCP, and the attenuation of DAP fluorescence was observed by the static quenching effect. In addition, the Cu 2+ @UiO-66-NH 2 /OPD loaded agarose hydrogel device can be used to detect DCP vapor with naked eyes and showed satisfactory detection result (LOD: 6.65 ppb).

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Nano Energy · 2023 · IF 17.6

High-performance piezoelectric nanogenerators based on Cs2Ag0.3Na0.7InCl6 double perovskites with high polarity induced by Zr/Te codoping

Xiangcong He,Jinju Zheng,Tao Yang,Deliu Ou,Chris R. Bowen,Songhan Shi,Qiaochu Chen,Hui Fu,Shuangwu Huang,Yumin Ye,Xiaocheng Huang,Wenna Liu,Weiyou Yang

Piezoelectric nanogenerators (PENGs), which operate based on mechanical-to-electrical energy conversion, have been widely explored for exciting applications in modern devices such as wearable electronics , self-powered sensors, and energy harvesters . Herein, we report on high-performance PENGs based on Cs 2 Ag 0.3 Na 0.7 InCl 6 double perovskite (CDP) within a polyvinylidene fluoride (PVDF) matrix, which exhibit enhanced polarity due to rationally designed Zr/Te codoping. As a proof of concept , the resultant PENGs based on Zr/Te codoped CDP@PVDF deliver an excellent piezoelectric output, with a maximum open-circuit voltage and short-circuit current density of 67 V and 18 μA·cm −2 . This level of performance is ∼19 and ∼12 times higher than PVDF-based PENGs with no CDP, and ∼2 and ∼4 times higher than CDP@PVDF-based PENGs without doping or with single Te doping, and ∼1 and ∼2 times higher than CDP@PVDF-based PENGs with single Zr doping, respectively. Moreover, the as-assembled PENGs exhibit impressive potential in wearable energy harvesters, motion sensors, and DC-power devices with robust stability, underscoring their bright future toward practical applications.

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Journal of Cleaner Production · 2022 · IF 11.072

Synthesis of Al–Zr master alloy in KF–AlF3–ZrO2 melts by aluminothermic reduction–molten salt electrolysis

Liyu Chen,Jiaxin Yang,Yifan Zhang,Shaohua Wu,Youjian Yang,Wenju Tao,Zhaowen Wang

The synthesis of an Al–Zr master alloy in KF–AlF 3 –ZrO 2 molten salt by combining aluminothermic reduction and molten salt electrolysis processes was studied. The effects of reduction parameters such as stirring, reaction time, Al/ZrO 2 mass ratio and temperature on the Zr content and Zr recovery rate were studied and optimized. Under the optimal conditions of stirring, reaction time of 4 h, Al/ZrO 2 mass ratio of 3 and temperature of 960 °C, an Al–Zr master alloy can be obtained with a Zr content of 6.78 wt% and Zr recovery rate of 29.85%. The characterization results of the alloy show that the main phases contain Al and Al 3 Zr. And the Al 3 Zr appears as long rod-shaped or tetragonal shapes, which influenced by the Zr content and cooling rate. In addition, the reduced molten salt is electrolyzed to further extract Zr from the molten salt. The results show that the Zr remaining in the molten salt is completely recovered with a Zr recovery rate up to 94.72%. This two-step process is feasible for the large-scale extraction of Zr in molten salts to produce Al–Zr master alloys.

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JOURNAL OF CATALYSIS · 2022 · IF 8.047

Catalytic hydrogenation of maleic anhydride to γ-butyrolactone over a high-performance hierarchical Ni-Zr-MFI catalyst

Haoyu Li,Pengfei Wu,Xianquan Li,Jifeng Pang,Shangru Zhai,Tao Zhang,Mingyuan Zheng

High-performance MFI zeolite supported nickel catalysts were prepared by the ammonia evaporation method for maleic anhydride (MA) conversion to γ-butyrolactone (GBL). According to comprehensive characterizations, the Ni catalysts possessed petal-like morphology and hierarchical structures with meso and micro pores. Nickel species were highly dispersed on the silica support and generated abundant Lewis acid sites (LAS), which effectively activated carbonyl groups in the reactant and accounted for the high activity in MA hydrogenation. Zr species hydrothermally introduced into the catalyst increased the number of LAS and decreased the apparent activation energy for the reaction. The highest GBL yield reached 95.6% over 40Ni-2Zr-MFI with the assistance of 3A zeolite to in-situ remove water byproduct. The catalyst showed reasonably good stability in five-cycle operation thanks to the strong interaction between Ni and support. The reaction route for MA hydrogenation was investigated, in which succinic anhydride (SA-A) served as the major reaction intermediate for GBL formation.

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Journal of Environmental Sciences · 2022 · IF 6.796

Selective removal of heavy metals by Zr-based MOFs in wastewater: New acid and amino functionalization strategy

Ping Chen,Yalan Wang,Xiaoqin Zhuang,Haijin Liu,Guoguang Liu,Wenying Lv

Zr-based metal-organic frameworks (MOFs) have been developed in recent years to treat heavy metals, e.g. hexavalent chromium Cr 6+ pollution, which damages the surrounding ecosystem and threaten human health. This kind of MOF is stable and convenient to prepare, but has the disadvantage of low adsorption capacity, limiting its wide application. To this end, a novel formic acid and amino modified MOFs were prepared, referred to as Form-UiO-66-NH 2 . Due to the modification of formic acid, its specific surface area, pore size, and crystal size were effectively expanded, and the adsorption capacity of Cr 6+ was significantly enhanced. Under optimal conditions, Form-UiO-66-NH 2 exhibited an excellent adsorption capacity (338.98 mg/g), ∼10 times higher than that reported for unmodified Zr-based MOFs and most other adsorbents. An in-depth study on the photoelectronic properties and pH confirmed that the adsorption mechanism of Form-UiO-66-NH 2 to Cr 6+ was electrostatic adsorption. After modification, the improvement of Cr 6+ adsorption capacity by Form-UiO-66-NH 2 was attributed to the expansion of its specific surface area and the increase in its surface charge. The present study revealed an important finding that Form-UiO-66-NH 2 elucidated selective adsorption to Cr 6+ in mixed wastewater containing toxic heavy metal ions and common nonmetallic water quality factors . This research provided a new acid and amino functionalization perspective for improving the adsorption capacity of Zr-based MOF adsorbents while simultaneously demonstrating their pertinence to target contaminant adsorption.

CAS / MDL: 64-18-6 10026-11-6
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RENEWABLE ENERGY · 2021 · IF 8.001

Synthesis of CaO/ZrO2 based catalyst by using UiO–66(Zr) and calcium acetate for biodiesel production

Hui Li,Yongbo Wang,Xiaoling Ma,Min Guo,Yan Li,Guoning Li,Ping Cui,Shoujun Zhou,Mingzhi Yu

Ca 2+ ion leaching and poor pore structure are obstacles of CaO for biodiesel production . To this end, a typical Zr–based metal organic framework, UiO–66(Zr) is adopted to support calcium acetate to prepare CaO/ZrO 2 catalyst. For comparison, catalyst precursor is activated in nitrogen (UCN) and air (UCA) atmosphere, respectively. Preparation factors including calcium acetate addition and activation temperature are evaluated. Moreover, effects of transesterification parameters on oil conversion are investigated and the optimized parameters are further used to examine catalyst reusability . Meanwhile, catalysts are characterized with TG, XRD, XPS , FTIR, Hammett indicator titration, N 2 adsorption and desorption. Results reveal UCN calcined at 650 °C (UCN650) and UCA calcined at 700 °C (UCA700) separately exhibits the best catalytic performance. The maximum conversion of 96.99% is achieved by UCN650 with catalyst amount of 6 wt% and molar ratio of methanol to oil of 9 at 65 °C for 60 min. Even after being used 3 cycles, conversion of 92.76% is still achieved by UCN650. By contrast, UCA700 shows lower conversion of 92.94% at the first cycle with catalyst amount of 8 wt% and molar ratio of methanol to oil of 9 at 65 °C for 60 min.

CAS / MDL: 10026-11-6
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JOURNAL OF SOLID STATE CHEMISTRY · 2021 · IF 3.498

Amino-functionalized Zr (IV) metal-organic polyhedron as water-stable catalyst for the photocatalytic degradation of tetracycline

He Huang,Zhao-Yang Liu,Shuang-Bao Li,Juan Zhu,Bao-Xu Jiang,Yu-Teng Zhang

In this work, an amino-functionalized Zr-based metal-organic polyhedron (denoted ZrT-1-NH 2 ), synthesised under the solvothermal method , has been selected as the photocatalyst for the removal of tetracycline (TC). The effects of adding dosages, pH values of TC degradation efficiency were investigated, and the results showed that this material was better effective in photocatalysis degradation of tetracycline antibiotic. In addition, the trapping experiments reveal that hydroxyl radical (•OH) and superoxide radical (•O 2 − ), serving as active species, play major roles in the photocatalytic process. Furthermore, a possible mechanism for the photocatalytic process is proposed. This work presents that zirconium-based metal-organic polyhedra (Zr-MOPs) may be promising photocatalysts for the removal of antibiotics in wastewater.

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FOOD CHEMISTRY · 2023 · IF 8.8

One-pot synthesis of nano Zr-based metal-organic frameworks for fluorescence determination of quercetin and Hg2+

Shitao Feng,Furong Tang,Fengshou Wu,Juan Zhang

In this study, a nanoscale Zr-based metal–organic framework (nano-Zr-MOF) was prepared by one-pot method using meso -tetra(4-carboxyphenyl)porphyrin as organic ligand and Zr 4+ as metal unit. The nanoscale structure endows it with excellent dispersion in water. The nano-Zr-MOF exhibited intense red fluorescence, which could be significantly quenched by the addition of quercetin , probably due to its electron-rich framework. The high selectivity for quercetin detection was verified with analogues and common ions as interfering agents. Moreover, the nano-Zr-MOF could be used as a highly selective and sensitive sensor for the detection of Hg 2+ . The detection limits for quercetin and Hg 2+ were 0.026 μM and 0.039 μM, respectively. This fluorometric method was successfully applied to detect quercetin in red wine and food samples with satisfactory recoveries ranging from 83.7–112.3% and 81.8–115.9%, respectively. The recovery in detection of Hg 2+ in lake water were ranging from 97.1–109.2%.

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JOURNAL OF THE AMERICAN CERAMIC SOCIETY · 2026 ·Vol. 109 ·期 9 ·e71223 · IF 4.2

Effect of Hf/Zr Ratio on Mechanical Properties and High-Temperature Performance of A6Ta2O17 Thermal Barrier Coatings

Shenxiang Luo,Xiaopeng Hu,Junyao Wu,Qing Liu,Sai Liu,Jinwei Guo,Fan Zhang,Wang Zhu

A series of A 6 Ta 2 O 17 /8YSZ double-ceramic-layer thermal barrier coatings (TBCs) with varying Hf/Zr molar ratios (1:2, 1:1, and 2:1) are fabricated via atmospheric plasma spraying (APS). The effect of the Hf/Zr ratio on the microstructure, mechanical properties, and high-temperature performance of the coatings under both thermal cycling and thermal shock conditions is systematically investigated. As Hf content increases, the nano-hardness decreases markedly from 16.5 to 12.8 GPa, whereas the intrinsic elastic modulus shows a modest increase from 222.8 to 232.8 GPa. Concurrently, the interfacial fracture toughness decreases from 0.96 to 0.62 MPa·m 1/2 . The equimolar H1Z1 coating (Hf/Zr = 1:1) demonstrates the highest thermal cycling resistance (2371 cycles), a performance attributed to a failure mechanism involving multi-channel stress release at the interfaces. Under thermal shock conditions, the H1Z1 coating also exhibits a prolonged thermal shock lifetime of 2180 cycles. In contrast, the Hf-rich composition (Hf/Zr = 2:1) fails catastrophically after only 682 cycles, due to insufficient erosion resistance, marked by pit formation and progressive thinning. These results highlight the equimolar H1Z1 coating as offering an optimal balance of mechanical compatibility and service durability, making it the most promising candidate among the investigated compositions for advanced TBCs applications.

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