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DALTON TRANSACTIONS · 2017 ·Vol. 46 ·期 22 ·7210-7218 · IF 4.029

Extraction behaviour and mechanism of Pt(IV) and Pd(II) by liquid–liquid extraction with an ionic liquid [HBBIm]Br

Wenhui Liu,Qi Wang,Yan Zheng,Shubin Wang,Yan Yan,Yanzhao Yang

In this study, a method of one-step separation and recycling of high purity Pd(II) and Pt(IV) using an ionic liquid, 1-butyl-3-benzimidazolium bromate ([HBBIm]Br), was investigated. The effects of [HBBIm]Br concentration, initial metal concentration, and loading capacity of [HBBIm]Br were examined in detail. It was observed that [HBBIm]Br was a very effective extractant for selectively extracting Pd(II) and precipitating Pt(IV). Through selectively extracting Pd(II) and precipitating Pt(IV), each metal with high purity was separately obtained from mixed Pd(II) and Pt(IV) multi-metal solution. The method of one-step separation of Pd(II) and Pt(IV) is simple and convenient. The anion exchange mechanism between [HBBIm]Br and Pt(IV) was proven through Job's method and FTIR and 1H NMR spectroscopies. The coordination mechanism between [HBBIm]Br and Pd(II) was demonstrated via single X-ray diffraction and was found to be robust and distinct, as supported by the ab initio quantum-chemical studies. The crystals of the [PdBr2 ·2BBIm] complex were formed first. Moreover, the influence of the concentrations of hydrochloric acid, sodium chloride, and sodium nitrate on the precipitation of Pt(IV) and extraction of Pd(II) was studied herein. It was found that only the concentration of H+ could inhibit the separation of Pt(IV) because H+ could attract the anion PtCl62−; thus, the exchange (anion exchange mechanism) between the anions PtCl62− and Br− was prevented. However, both the concentration of H+ and Cl− can obviously inhibit the extraction of Pd(II) because H+ and Cl− are the reaction products and increasing their concentration can inhibit the progress of the reaction (coordination mechanism).

研究领域: 化学 · 材料科学
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JOURNAL OF MEDICINAL CHEMISTRY · 2025 · IF 6.8

Fluoxetine-Conjugated Platinum(IV) Prodrugs Targeting eEF2K and Conquering Multidrug Resistance against Triple-Negative Breast Cancer

Jia-Qian Wang,Xiao-Meng Liu,Zi-Shuo Zhu,Zhe Li,Cheng-Zhi Xie,Xin Qiao,Yu-Kuan Feng,Jing-Yuan Xu

Triple-negative breast cancer (TNBC) poses formidable challenges in the clinic owing to its particularly malignant and aggressive properties. Overexpression of eukaryotic elongation factor-2 kinase (eEF2K) is highly correlated with the poor prognosis of TNBC, representing a promising therapeutic target. Herein, Fluoxetine as eEF2K-inhibitor and chemosensitizer was conjugated with cisplatin/oxaliplatin to present two-in-one prodrugs 8–19. Multievaluation indicated that monosubstituted 8 and disubstituted 12 exhibited 407- and 174-fold higher cytotoxicity than cisplatin against MDA-MB-231 cells by elevating DNA damage-induced apoptosis and eEF2K-triggered autophagy. Moreover, 8 and 12 significantly overcame chemoresistance in A549cisR cells, evidenced by downregulating resistance-related key proteins P-gp, GST-π, ATM, and RAD51. Syngeneic and xenograft mouse models demonstrated that 8 and 12 could effectively inhibit tumor growth and metastasis, and reduce toxicity compared to cisplatin in vivo. Additionally, 8 and 12 stimulated immunomodulation including T-cell proliferation and Th1 cytokine production. All results hold the promise of 8 and 12 as multifunctional chemotherapeutic agents.

研究领域: 肿瘤学 · 药理学 · 分子生物学
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MOLECULAR PHARMACEUTICS · 2020 · IF 4.321

Delivery of Platinum(IV) Prodrugs via Bi2Te3 Nanoparticles for Photothermal–Chemotherapy and Photothermal/Photoacoustic Imaging

Yan Ma,Dong-Yang Zhang,Zhuo Peng,Shixia Guan,Junqiu Zhai

Combinational administration of photothermal therapy (PTT) and chemotherapy (CT) shows great potential in improving the efficiency of tumor treatment. Herein, we designed a novel nanocomposite Pt@Bi2Te3 composed of bismuth telluride (Bi2Te3) nanoparticles and platinum(IV) prodrugs (Pt) for PTT–CT combination therapy. The obtained Bi2Te3 was synthesized by a simple solvothermal method and modified by polyethylene glycol, which exhibited excellent photothermal (PT) efficiency and stability and could also serve as a bimodal bioimaging contrast agent in PT and photoacoustic (PA) imaging. In vitro experiment results showed that the nanocomposite Pt@Bi2Te3 could effectively increase the uptake of platinum in cancer cells, which could kill tumor cells through the combined effect of PTT and CT. Furthermore, combination therapy of cancer in vivo was achieved with obvious tumor-growth inhibition without inducing observed side effects. We revealed the great potential of Bi2Te3 nanocomposites in increasing therapeutic efficiency by PTT–CT therapy and PA–PT imaging.

研究领域: 肿瘤学 · 生物医学工程 · 材料科学
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NEW JOURNAL OF CHEMISTRY · 2022 ·Vol. 46 ·期 16 ·7695-7703 · IF 3.925

Successive preconcentration and mechanistic investigation of Au(III), Pd(II), Pt(IV) and Rh(III) via cloud point extraction using a functionalised ionic liquid

Qi Wu,Changfeng Zhao,Qinzhong Wang,Jing Liu

This study proposes the efficient separation of Au(III)/Pd(II)/Pt(IV)/Rh(III) through the 2-mercaptobenzothiazole-functionalised ionic liquid ([C6mim][2MBT]) using a cloud point extraction system. Direct cloud point extraction of Au(III) (about 99.9%) was realised without involving any functionalised ionic liquids. A significant enhancement of the Pd(II) extraction performance was found by adding rationally constructed [C6mim][2MBT]. Consequently, a fairly high extraction percentage of about 99.4% was obtained. However, further advancement of the proposed cloud point extraction showed that it could not be applied for the preconcentration of Pt(IV) and Rh(III) without adding stannous chloride, which plays a critical role in the segregation and could be adjusted by changing the hydrochloric acid concentration. Under the optimised conditions, the Rh(III) extraction process shows a high yield percentage (ca. 83.0%), where the majority of Pt(IV) was enriched in the aqueous phase. In addition, the underlying possible extraction mechanism was investigated using UV-vis, FT-IR and TEM measurements, which indicated that TX-114 acted as a solvent for the extracted metals. The developed procedure reveals efficient direct Au(III)/Pd(II)/Pt(IV)/Rh(III) separation using [C6mim][2MBT] via cloud point extraction.

CAS / MDL: 171058-17-6
研究领域: 分析化学 · 环境科学
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APPLIED ORGANOMETALLIC CHEMISTRY · 2022 ·Vol. 36 ·期 7 ·e6759 · IF 4.072

Synthesis, characterization, and antitumor biological evaluation of novel fluorine-containing platinum (IV) complexes

Lihua Chen,Pan Zhao,Jing Yang,Xiali Liao,Bo Yang,Chuanzhu Gao

A series of antitumor platinum (IV) complexes based on ammonia and fluoropyridine carrier groups with biotin and chloride ions as axial groups have been designed and synthesized in this paper. The structures of platinum (IV) complexes were fully characterized by 1 H NMR, ESI-MS, and IR. Such Pt (IV) complexes have certain tumor targeting properties, and the Pt (II) complexes released in the reducing microenvironment could combine with DNA. Compared with cisplatin, complexes S3 and S4 exhibited similar cytotoxicity against SW480, HCT116, and HepG2 cancer cell lines according to in vitro antitumor activity evaluation. Particularly, Complex S2 showed 1.5–3.0 times higher cytotoxicity than cisplatin and picoplatin against selected cell lines. According to the structure–activity relationship, the introduction of fluorine atoms and axial chloride has an important influence on the strong cytotoxic activity of Pt (IV) complex. In addition, the axial biotin molecule increased the targeting of the complex to tumor cells. Overall, the novel fluorine-containing Pt (IV) complex S2 is an attractive antitumor lead compound with further research value.

研究领域: 药物化学 · 肿瘤学 · 生物无机化学
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JOURNAL OF MOLECULAR LIQUIDS · 2022 · IF 6.633

A separation strategy of Au(III), Pd(II) and Pt(IV) based on hydrophobic deep eutectic solvent from hydrochloric acid media

Ronghao Liu,Jinjie Hao,Yangyang Wang,Yuanyuan Meng,Yanzhao Yang

A hydrophobic deep eutectic solvent (HDES) based on lidocaine and thymol was examined for selective extraction and separation of Au(III), Pd(II) and Pt(IV) in the acidic leaching solution of secondary resources. At first, the properties of HDES were characterized by 1 H NMR, DSC, TGA, RDF and ESP to prove its suitability for extraction process. In addition, extraction behaviors, maximum extraction capacities and competitive extraction experiment were investigated to explore the extraction ability of HDES. The results show that the maximum extraction capacity of Au(III), Pd(II) and Pt(IV) reached 761.2 g/L, 98.3 g/L and 299.3 g/L, respectively. Meanwhile, their extraction efficiency was affected by the changing acidity of aqueous. And then, ion-association mechanism in the extraction process was proposed through the analysis of FT-IR. Finally, a separation process was proposed for the recovery of Au(III), Pd(II) and Pt(IV) based on acidity control and KSCN, which achieved recovery efficiency of 97.8 % Au(III), 99.9 % Pd(II) and 89.5 % Pt(IV). After collecting and regenerating the used HDES, their extraction performance of Au(III), Pd(II) and Pt(IV) were still maintained.

研究领域: 化学工程 · 材料科学
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Polymers · 2022 ·Vol. 14 ·期 2 ·287 · IF 4.967

NIR and Reduction Dual-Sensitive Polymeric Prodrug Nanoparticles for Bioimaging and Combined Chemo-Phototherapy

Shuying Li,Yanjuan Wu,Xiukun Xue,Siyuan Liu

The combination of chemotherapy, photothermal therapy (PTT) and photodynamic therapy (PDT) based on a single nanosystem is highly desirable for cancer treatment. In this study, we developed a versatile Pt(IV) prodrug-based nanodrug, PVPt@Cy NPs, to realize synchronous chemotherapy, PDT and PTT and integrate cancer treatment with bioimaging. To construct PVPt@Cy NPs, the amphiphilic Pt(IV)-based polymeric prodrug PVPt was synthesized by a facile one-pot coupling reaction, and then it was used to encapsulate an optotheranostic agent (HOCyOH, Cy) via hydrophobic interaction-induced self-assembly. These NPs would disaggregate under acidic, reductive conditions and NIR irradiation, which are accompanied by photothermal conversion and reactive oxygen species (ROS) generation. Moreover, the PVPt@Cy NPs exhibited an enhanced in vitro anticancer efficiency with 808-nm light irradiation. Furthermore, the PVPt@Cy NPs showed strong NIR fluorescence and photothermal imaging in H22 tumor-bearing mice, allowing the detection of the tumor site and monitoring of the drug biodistribution. Therefore, PVPt@Cy NPs displayed an enormous potential in combined chemo-phototherapy.Keywords:combined chemo-phototherapy;Pt(IV) prodrug;nanoparticle;bioimaging

研究领域: 肿瘤学 · 药剂学 · 生物医学工程
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ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH · 2023 ·Vol. 30 ·期 35 ·84609-84619 · IF 5.8

Functionalization of melamine sponge for the efficient recovery of Pt(IV) from acid leachates

Wu Zhaojiang,Lin Zheng,Wang Shengye,Yang Bo,Xiao Ke

The recovery of platinum from industrial waste is of critical importance. Usually, the recovery method is to dissolve the solid waste with acid to form a solution where platinum mainly exists in the form of Pt(IV). Therefore, it is urgent to efficiently and selectively adsorb Pt(IV) ions from acid leachates. In this study, a highly efficient adsorbent was developed by grafting of carboxyl and amine groups onto melamine sponge with alginate-Ca and polyethylenimine-glutaraldehyde (ML/ACPG). Combination of SEM, FTIR and XPS showed that the ML/ACPG sponge had a tree structure and the amino, carboxyl and hydroxyl groups were successfully introduced. Maximum adsorption capacity of ML/ACPG sponge reached up to 101.1 mg/L at pH of 1 (optimum initial pH value). The Pt(IV) ions were readily desorbed (within 60–80 min) using 0.1 M HCl + 0.025 M thiourea solution. Desorption efficiency remained higher than 83.3% while adsorption capacity decreased by less than 6.0% after 5 cycles operation. The ML/ACPG sponge was stable in 3 M of HNO 3 , NaCl after shaking for 72 h at 300 rpm with mass loss less than 2.5%. The mechanism of Pt(IV) adsorption onto ML/ACPG sponge mainly involved coordination by electrostatic attraction and carboxyl groups by protonated amine groups. The above results confirmed that the ML/ACPG sponge has a good practical application potential for Pt(IV) recovery from acid leachates.

研究领域: 材料科学 · 环境工程
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Journal of the Iranian Chemical Society · 2023 ·Vol. 20 ·期 11 ·2861-2870 · IF 2.4

Three-dimensional self-assembled reduced graphene oxide composite as a promising adsorbent for the collection of palladium (II) and platinum (IV) in a low concentration

Chen Lei,Li Yuan-Long,Li Rong-Xin,Shu Qi-Jiang,Yang Tao

A three-dimensional reduced graphene oxide aerogel modified by sulfamic acid and ethylenediamine was prepared via one-step reduction self-assembly under atmospheric pressure within 90 °C heating constantly. The adsorption efficiency of palladium (II) was ~ 97.0% at pH 11 within 50 min by the prepared composite. While the composite exhibited adsorption for platinum (IV) at acid condition, giving a rising to an adsorption efficiency was 61.7% at pH 5. Only 25.8% adsorption efficiency of platinum (IV) was found at pH 11, and 17.0% adsorption efficiency of palladium (II) was obtained at pH 5. The adsorption capacity of the composite for palladium (II) was 80 μg mg −1 above, and the adsorption capacity of the composite for platinum (IV) was ~ 160 μg mg −1 . The obtained palladium (II) and platinum (IV) can be eluted by urea and surfactant from the surface of the composite, respectively. Understanding the mechanism of the adsorption/desorption between palladium (II)/platinum (IV) and the composite, explored a promising way for recycling and enrichment of noble metal at a low concentration.

研究领域: 材料科学 · 环境科学
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JOURNAL OF MOLECULAR LIQUIDS · 2019 · IF 4.561

Extraction and stripping of platinum (IV) from acidic chloride media using guanidinium ionic liquid

Ning Wang,Qi Wang,Wenjuan Lu,Miaoyan Ru,Yanzhao Yang

The extraction and stripping behaviors of Pt(IV) from acidic chloride media by 2,2-diheptyl-1,1,3,3-tetramethylguanidinium bromide were investigated. The extraction of Pt(IV) was carried out by modulating various parameters such as concentration of the extractant, temperature, and concentration of HCl solution. Based on the characterization of experimental results such as Job's method data, UV–vis spectra and fourier transform infrared spectra analysis, the anion exchange mechanism was confirmed. Quantum chemical calculations were performed to provide theoretical support for the mechanism. The ionic liquid showed outstanding selectivity for Pt(IV) over the base metals. Furthermore, the organic phase could be easily used for four extraction-stripping cycles by reductive stripping process using 0.5 M CS(NH 2 ) 2 /0.5 M HCl. The numbers of theoretical stages needed for the effective extraction and stripping of Pt(IV) has been determined by McCabe Thiele's diagram. Under the selected counter-current extraction and stripping stages, the extraction efficiency and stripping efficiency could reach 99.5% and 99.0%, respectively. Therefore, the system is highly effective, selective and recyclable to extract Pt(IV). On the basis of the extraction protocol, the system may be a promising candidate for highly selective extraction of Pt(IV).

研究领域: 化学工程 · 材料科学
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Journal of Materials Chemistry B · 2022 ·Vol. 10 ·期 7 ·1031-1041 · IF 7.571

A multifunctional platinum(IV) and cyanine dye-based polyprodrug for trimodal imaging-guided chemo–phototherapy

Shuying Li,Yanjuan Wu,Siyuan Liu,Ting Wu,Guozheng Liu,Tianduo Li,Zhaowei Chen

Imaging-guided chemo–phototherapy based on a single nanoplatform has a great significance to improve the efficiency of cancer therapy and diagnosis. However, high drug content, no burst release and real-time tracking of nanodrugs are the three main challenges for this kind of multifunctional nanotheranostics. In this work, we developed an innovative theranostic nanoplatform based on a Pt(IV) prodrug and a near-infrared (NIR) photosensitizer. A Pt(IV) prodrug and a cyanine dye (HOCyOH, Cy) were copolymerized and incorporated into the main chain of a polyprodrug (PCPP), which self-assembled into nanoparticles (NPs) with ∼27.61% Cy loading and ∼9.37% Pt loading, respectively. PCPP NPs enabled reduction-triggered backbone cleavage of polyprodrugs and bioactive Pt(II) release; Cy could be activated under 808 nm laser irradiation to produce local hyperthermia and reactive oxygen species (ROS) for phototherapy. Moreover, PCPP NPs with extremely high Cy and Pt heavy metal contents in the backbone of the polyprodrug could directly track the nanodrugs themselves via near-infrared fluorescence (NIRF) imaging, photothermal imaging, and computed tomography (CT) imaging in vitro and in vivo. As revealed by trimodal imaging, PCPP NPs were found to exhibit excellent tumor accumulation and antitumor efficiency after intravenous injection into H22-tumor-bearing mice. The dual-drug backboned polyprodrug nanoplatform exhibited great potential for bioimaging and combined chemo–phototherapy.

研究领域: 肿瘤学 · 生物医学工程 · 药剂学
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Frontiers in Bioengineering and Biotechnology · 2023 · IF 5.7

A pH-responsive liposomal nanoplatform for co-delivery of a Pt(IV) prodrug and cinnamaldehyde for effective tumor therapy

Tang Ting,Gong Yufang,Gao Yuan,Pang Xinlong,Liu Shuangqing,Xia Yulan,Liu Dongsheng,Zhu Lin,Fan Qing,Sun Xiao

Introduction: The tumor microenvironment (TME) is mainly characterized by abnormally elevated intracellular redox levels and excessive oxidative stress. However, the balance of the TME is also very fragile and susceptible to be disturbed by external factors. Therefore, several researchers are now focusing on intervening in redox processes as a therapeutic strategy to treat tumors. Here, we have developed a liposomal drug delivery platform that can load a Pt(IV) prodrug (DSCP) and cinnamaldehyde (CA) into a pH-responsive liposome to enrich more drugs in the tumor region for better therapeutic efficacy through enhanced permeability and retention effect.Methods: Using the glutathione-depleting properties of DSCP together with the ROS-generating properties of cisplatin and CA, we synergistically altered ROS levels in the tumor microenvironment to damage tumor cells and achieve anti-tumor effects in vitro.Results: A liposome loaded with DSCP and CA was successfully established, and this liposome effectively increased the level of ROS in the tumor microenvironment and achieved effective killing of tumor cells in vitro.Conclusion: In this study, novel liposomal nanodrugs loaded with DSCP and CA provided a synergistic strategy between conventional chemotherapy and disruption of TME redox homeostasis, leading to a significant increase in antitumor effects in vitro.

研究领域: 药剂学 · 肿瘤学 · 纳米医学
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