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1.
Rui Cao Wen Sun Zheng Zhang Xiaojing Li Jianjun Du Jiangli Fan Xiaojun Peng 《中国化学快报》2021,31(12):3127-3130
Chemodynamic therapy (CDT) refers to generating hydroxyl radical (·OH) in tumor sites via hydrogen peroxide (H2O2) catalyzed by transition metal ions in cancer cells under acidic environment. However, H2O2 content is not enough for effective CDT, although H2O2 content in cancer cells is higher than that of normal cells. Herein, we synthesized DOX@BSA-Cu NPs (nanoparticles) for effective CDT by providing enhanced content of H2O2 in cancer cells. The results proved Cu2+ in NPs could be reduced to Cu+ by glutathione (GSH) and effectively converted H2O2 to ·OH. Moreover, the loaded low-dose doxorubicin (DOX) in the NPs could improve the content of H2O2 and resulted in more efficient generation of ·OH in cancer cells. Thus DOX@BSA-Cu NPs exhibited higher cytotoxicity to cancer cells. This research may provide new ideas for the further studies on more effective Cu(II)-based CDT nanoagents. 相似文献
2.
Chemodynamic therapy(CDT) is an emerging endogenous stimulation activated tumor treatment approach that exploiting iron-containing nanomedicine as catalyst to convert hydrogen peroxide(H_2O_2)into toxic hydroxyl radical(·OH) through Fenton reaction.Due to the unique characteristics(weak acidity and the high H_2O_2 level) of the tumor microenvironment,CDT has advantages of high selectivity and low side effect.However,as an important substrate of Fenton reaction,the endogenous H_2O_2 in tumor is still insufficient,which may be an important factor limiting the efficacy of CDT.In order to optimize CDT,various H_2O_2-generating nanomedicines that can promote the production of H_2O_2 in tumor have been designed and developed for enhanced CDT.In this review,we summarize recently developed nanomedicines based on catalytic enzymes,nanozymes,drugs,metal peroxides and bacteria.Finally,the challenges and possible development directions for further enhancing CDT are prospected. 相似文献
3.
以乙酰丙酮铜和硫粉为铜源和硫源,在油酸(OA)-油胺(OM)-十八烯(ODE)体系中合成了近红外吸收的硫化铜(CuS)纳米颗粒,并通过改变硫元素活化状态的方式调节其吸收峰到适合光热治疗的1 064 nm附近。通过阳离子交换法进一步制备了Fe、Mn等元素掺杂的CuS纳米颗粒,并保持其吸收峰位置几乎不变。使用微乳法进行聚乙二醇(PEG)化修饰后,这些纳米颗粒在水溶液中表现出良好的分散性和稳定性。分别测试了CuS纳米颗粒在Fe3+掺杂前后的光热性能及羟基自由基(·OH)生成能力。结果表明,PEG修饰后Fe3+掺杂的CuS纳米颗粒(CuS∶Fe-PEG)在1 064 nm处的质量消光系数为37.5 L·g-1·cm-1,光热转换效率可达43.7%。虽然光热性能略低于未掺杂的CuS-PEG,但其·OH生成能力有大幅提升。细胞实验也表明,在弱酸性条件下,CuS∶Fe-PEG具有更好的肿瘤细胞抑制能力,在1 064 nm激光照射下能够有效杀死肿瘤细胞,可用于光热/化学动力学联合治疗。 相似文献
4.
以乙酰丙酮铜和硫粉为铜源和硫源,在油酸(OA)-油胺(OM)-十八烯(ODE)体系中合成了近红外吸收的硫化铜(CuS)纳米颗粒,并通过改变硫元素活化状态的方式调节其吸收峰到适合光热治疗的1064 nm附近。通过阳离子交换法进一步制备了Fe、Mn等元素掺杂的CuS纳米颗粒,并保持其吸收峰位置几乎不变。使用微乳法进行聚乙二醇(PEG)化修饰后,这些纳米颗粒在水溶液中表现出良好的分散性和稳定性。分别测试了CuS纳米颗粒在Fe3+掺杂前后的光热性能及羟基自由基(·OH)生成能力。结果表明,PEG修饰后Fe3+掺杂的CuS纳米颗粒(CuS∶Fe-PEG)在1064 nm处的质量消光系数为37.5 L·g-1·cm-1,光热转换效率可达43.7%。虽然光热性能略低于未掺杂的CuS-PEG,但其·OH生成能力有大幅提升。细胞实验也表明,在弱酸性条件下,CuS∶Fe-PEG具有更好的肿瘤细胞抑制能力,在1064 nm激光照射下能够有效杀死肿瘤细胞,可用于光热/化学动力学联合治疗。 相似文献
5.
以铪簇作为金属有机骨架的连接点、刚性双羧基配体2,2’-联吡啶-5,5’-二羧酸作为连接器、乙酸或三氟乙酸和水作为结构调节剂,通过溶剂热法合成得到八面体结构(Hf-MOFs-1)和片状结构(Hf-MOFs-2)的铪基纳米金属有机骨架(Hf-nMOFs),再经Fe3+修饰得到多功能金属有机骨架材料(Hf-Fe-MOFs-1和Hf-Fe-MOFs-2)。模拟肿瘤微环境体系中羟基自由基检测结果表明,X射线照射能显著促进Hf-Fe-MOFs-1和Hf-Fe-MOFs-2材料产生羟基自由基,且片状Hf-Fe-MOFs-2羟基自由基产生能力高于八面体Hf-Fe-MOFs-1。进一步地,在细胞层面证实了材料能够成功被细胞摄入并实现低剂量X射线促进的化学动力学协同治疗。 相似文献
6.
以铪簇作为金属有机骨架的连接点、刚性双羧基配体2,2''-联吡啶-5,5''-二羧酸作为连接器、乙酸或三氟乙酸和水作为结构调节剂,通过溶剂热法合成得到八面体结构(Hf-MOFs-1)和片状结构(Hf-MOFs-2)的铪基纳米金属有机骨架(Hf-nMOFs),再经Fe3+修饰得到多功能金属有机骨架材料(Hf-Fe-MOFs-1和Hf-Fe-MOFs-2)。模拟肿瘤微环境体系中羟基自由基检测结果表明,X射线照射能显著促进Hf-Fe-MOFs-1和Hf-Fe-MOFs-2材料产生羟基自由基,且片状Hf-Fe-MOFs-2羟基自由基产生能力高于八面体Hf-Fe-MOFs-1。进一步地,在细胞层面证实了材料能够成功被细胞摄入并实现低剂量X射线促进的化学动力学协同治疗。 相似文献
7.
《中国化学快报》2020,31(10):2831-2834
This study demonstrated that as-synthesized nano Fe/Cu bimetals could achieve significant enhancement in the degradation of diclofenac (DCF), as compared to much slow removal of DCF by Cu(II) or zero valent iron nanoparticles (nZVI), respectively. Further observations on the evolution of O2 activation process by nano Fe/Cu bimetals was conducted stretching to the preparation phase (started by nZVI/Cu2+). Interesting breakpoints were observed with obvious sudden increase in the DCF degradation efficiency and decrease in solution pH, as the original nZVI just consumed up to Fe(II) and Cu(II) appeared again. It suggested that the four-electrons reaction of O2 and Cu-deposited nZVI would occur to generate water prior to the breakpoints, while Cu(0) and Fe(II) would play most important role in activation of O2 afterwards. Through the electron spin resonance (ESR) analysis and quenching experiments, OH was identified as the responsible reactive species. Further time-dependent quantifications in the cases of Cu(0)/Fe(II) systems were carried out. It was found that the OH accumulation was positively and linearly correlated with nCu dose, Fe(II) consumption, and Fe(II) dose, respectively. Since either Cu(0) or Fe(II) would be inefficient in activating oxygen to produce OH, a stage-evolution mechanism of O2 activated by nano Fe/Cu bimetals was proposed involving: (a) Rapid consumption of Fe(0) and release of Fe(II) based on the Cu-Fe galvanic corrosion, (b) adsorption and transformation of O2 to O22− at the nCu surface, and (c) Fe(II)-catalyzed activation of the adsorbed O22− to OH. 相似文献
8.
采用沉淀-沉积法制备了PdO/CeO2催化剂,并使用X射线衍射、高分辨透射电镜、N2吸附-脱附等温线、X射线光电子能谱和Raman光谱对催化剂进行了表征.表征结果显示, Pd在复合物中以Pd2+形式存在; PdO和CeO2间的相互作用提高了CeO2中的Ce3+含量.通过酸性橙7和水杨酸的类芬顿降解考察了PdO/CeO2的多相类芬顿和可见光芬顿催化活性.结果表明, PdO沉积显著地促进了水杨酸的类芬顿降解,催化剂的PdO含量为1.0 at%时其活性最佳.染料酸性橙7在可见光照射条件下会引发染料光敏化效应.吸附的染料分子在光激发后通过界面电子注入促进了Ce3+自表面过氧物种的再生.由此, PdO负载和可见光照射的共同作用下,1.0 PdO/CeO2催化剂的酸性橙7类芬顿降解速率常数为3.90 h-1,为纯CeO2活性的50倍左右. 相似文献
9.
采用沉淀-沉积法制备了PdO/CeO2催化剂,并使用X射线衍射、高分辨透射电镜、N2吸附-脱附等温线、X射线光电子能谱和Raman光谱对催化剂进行了表征.表征结果显示, Pd在复合物中以Pd2+形式存在; PdO和CeO2间的相互作用提高了CeO2中的Ce3+含量.通过酸性橙7和水杨酸的类芬顿降解考察了PdO/CeO2的多相类芬顿和可见光芬顿催化活性.结果表明, PdO沉积显著地促进了水杨酸的类芬顿降解,催化剂的PdO含量为1.0 at%时其活性最佳.染料酸性橙7在可见光照射条件下会引发染料光敏化效应.吸附的染料分子在光激发后通过界面电子注入促进了Ce3+自表面过氧物种的再生.由此, PdO负载和可见光照射的共同作用下,1.0 PdO/CeO2催化剂的酸性橙7类芬顿降解速率常数为3.90 h-1,为纯CeO2活性的50倍左右. 相似文献
10.
11.
Oximes were oxidized to the corresponding carbonyl compounds in good to high yields by environmentally friendly and green oxidant,H_2O_2 catalyzed by montmorillonite K-10 supported cobalt(Ⅱ) chloride. 相似文献
12.
Two new procedures were employed for studying the reaction of hydrogen atoms with hydrogen peroxide. The absorption in the UV-range was observed either for an acidic aqueous solution containing only hydrogen peroxide or for a similar solution but also containing an aliphatic alcohol. From the increase in absorption of various alcohol radicals, a rate constant of 3.5×107 dm3 mol−1 s−1 was determined. In addition, the rate constant for the reaction of hydroxyl radicals with hydrogen peroxide was determined to be 3.0×107 dm3 mol−1 s−1. 相似文献
13.
Jiajun Bi Jian Chen Yahao Dong Wen Guo Dajian Zhu Tao Li 《Journal of polymer science. Part A, Polymer chemistry》2018,56(20):2344-2353
A new polymer was prepared from 1,3,5-triformylphloroglucinol (noted as TDTB) and o-phenylenediamine through Schiff base condensation reaction, and palladium (II) was immobilized on the polymer (noted as TbPo-Pd(II)). This process was easy to work-up and cost-effective. The structure and composition of TbPo-Pd(II) were fully characterized by FTIR, TGA, XPS, AAS, SEM, and TEM analyses. Meanwhile, this catalyst showed desired thermal stability and excellent performance in water/methanol system for Suzuki and Sonogashira coupling reactions. In addition, this heterogeneous catalyst can be readily recovered by simple filtration with no appreciable Pd leaching in the reaction. This work provides a powerful protocol for rapid access to asymmetrical biphenyls and aryl alkynes. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2344–2353 相似文献
14.
A simple and sensitive method for the determination of nanomolar levels of hydrogen peroxide (H2O2) in seawater has been developed and validated. This method is based on the reduction of H2O2 by ferrous iron in acid solution to yield hydroxyl radical (OH) which reacts with benzene to produce phenol. Phenol is separated from the reaction mixture by reversed phase high performance liquid chromatography and its fluorescence intensity signals were measured at excitation and emission of 270 and 298 nm, respectively. Under optimum conditions, the calibration curve exhibited linearity in the range of (0-50) × 103 nmol L−1 H2O2. The relative standard deviations for five replicate measurements of 500 and 50 nmol L−1 H2O2 are 1.9 and 2.4%, respectively. The detection limit for H2O2, defined as three times the standard deviation of the lowest standard solution (5 nmol L−1 H2O2) in seawater is 4 nmol L−1. Interference of nitrite ion (NO2−) on the fluorescence intensity of phenol was also investigated. The result indicated that the addition of 10 μmol L−1 NO2− to seawater samples showed no significant interference, although, the addition of 50 μmol L−1 NO2− to the seawater samples decreases the fluorescence intensity signals of phenol by almost 40%. Intercomparison of this method with well-accepted (p-hydroxyphenyl) acetic acid (POHPAA)-FIA method shows excellent agreement. The proposed method has been applied on-board analysis of H2O2 in Seto Inland seawater samples. 相似文献
15.
Simple and fast spectrophotometric determination of H(2)O(2) in photo-Fenton reactions using metavanadate 总被引:1,自引:0,他引:1
This work proposes a spectrophotometric method for the determination of hydrogen peroxide during photodegradation reactions. The method is based on the reaction of H2O2 with amonium metavanadate in acidic medium, which results in the formation of a red-orange color peroxovanadium cation, with maximum absorbance at 450 nm. The method was optimized using the multivariate analysis providing the minimum concentration of vanadate (6.2 mmol L−1) for the maximum absorbance signal. Under these conditions, the detection limit is 143 μmol L−1. The reaction product showed to be very stable for samples of peroxide concentrations up to 3 mmol L−1 at room temperature during 180 h. For higher concentrations however, samples must be kept refrigerated (4 °C) or diluted. The method showed no interference of Cl− (0.2-1.3 mmol L−1), NO3− (0.3-1.0 mmol L−1), Fe3+ (0.2-1.2 mmol L−1) and 2,4-dichlorophenol (DCP) (0.2-1.0 mmol L−1). When compared to iodometric titration, the vanadate method showed a good agreament. The method was applied for the evaluation of peroxide consumption during photo-Fenton degradation of 2,4-dichlorophenol using blacklight irradiation. 相似文献
16.
Three malonato-bridged copper(II) complexes of the formulas [[Cu(H2O)3][Cu(C3H2O4)2(H2O)]]n (1), [[Cu(H2O)4]2[Cu(C3H2O4)2(H2O)]] [Cu(C3H2O4)2(H2O)2][[Cu(H2O)4][Cu(C3H2O4)2(H2O)2]] (2), and [Cu(H2O)4][Cu(C3H2O4)2(H2O)2] (3) (C3H2O4 = malonate dianion) have been prepared, and the structures of the two former have been solved by X-ray diffraction methods. The structure of compound 3 was already known. Complex 1 crystallizes in the orthorhombic space group Pcab, Z = 8, with unit cell parameters of a = 10.339(1) A, b = 13.222(2) A, and c = 17.394(4) A. Complex 2 crystallizes in the monoclinic space group P2/c, Z = 4, with unit cell parameters of a = 21.100(4) A, b = 21.088(4) A, c = 14.007(2) A, and beta = 115.93(2) degrees. Complex 1 is a chain compound with a regular alternation of aquabis(malonato)copper(II) and triaquacopper(II) units developing along the z axis. The aquabis(malonato)copper(II) unit acts as a bridging ligand through two slightly different trans-carboxylato groups exhibiting an anti-syn coordination mode. The four carboxylate oxygens, in the basal plane, and the one water molecule, in the apical position, describe a distorted square pyramid around Cu1, whereas the same metal surroundings are observed around Cu2 but with three water molecules and one carboxylate oxygen building the equatorial plane and a carboxylate oxygen from another malonato filling the apical site. Complex 2 is made up of discrete mono-, di-, and trinuclear copper(II) complexes of the formulas [Cu(C3H2O4)2(H2O)2]2-, [[Cu(H2O)4] [Cu(C3H2O4)2(H2O)2]], and [[Cu(H2O)4]2[Cu(C3H2O4)2(H2O)]]2+, respectively, which coexist in a single crystal. The copper environment in the mononuclear unit is that of an elongated octahedron with four carboxylate oxygens building the equatorial plane and two water molecules assuming the axial positions. The neutral dinuclear unit contains two types of copper atoms, one that is six-coordinated, as in the mononuclear entity, and another that is distorted square pyramidal with four water molecules building the basal plane and a carboxylate oxygen in the apical position. The overall structure of this dinuclear entity is nearly identical to that of compound 3. Finally, the cationic trimer consists of an aquabis(malonato)copper(II) complex that acts as a bismonodentate ligand through two cis-carboxylato groups (anti-syn coordination mode) toward two tetraaqua-copper(II) terminal units. The environment of the copper atoms is distorted square pyramidal with four carboxylate oxygens (four water molecules) building the basal plane of the central (terminal) copper atom and a water molecule (a carboxylate oxygen) filling the axial position. The magnetic properties of 1-3 have been investigated in the temperature range 1.9-290 K. Overall, ferromagnetic behavior is observed in the three cases: two weak, alternating intrachain ferromagnetic interactions (J = 3.0 cm-1 and alpha J = 1.9 cm-1 with H = -J sigma i[S2i.S2i-1 + alpha S2i.S2i+1]) occur in 1, whereas the magnetic behavior of 2 is the sum of a magnetically isolated spin doublet and ferromagnetically coupled di- (J3 = 1.8 cm-1 from the magnetic study of the model complex 3) and trinuclear (J = 1.2 cm-1 with H = -J (S1.S2 + S1.S3) copper(II) units. The exchange pathway that accounts for the ferromagnetic coupling, through an anti-syn carboxylato bridge, is discussed in the light of the available magneto-structural data. 相似文献
17.
Norberto González-Mojica Leticia Almazán-Sánchez Jesús G. García-Torres Ivette Santana-Martinez Diego Martínez-Otero Miguel A. Sánchez-Carmona 《合成通讯》2019,49(5):679-687
A collection of 1,2,3-triazole-3-oxides was obtained from oxidation of the corresponding 1,4-disubstituted-1,2,3-triazoles mediated by a H2O2–CF3CO2H system through a simple protocol in good yields showing high efficiency. 相似文献
18.
S. Y. Fredericks J. M. Pedulla K. D. Jordan T. S. Zwier 《Theoretical chemistry accounts》1997,96(1):51-55
The OH stretch IR spectrum of (H2O)3 is significantly altered upon complexation of the cluster with a benzene molecule. Theoretical calculations show that the
differences in the OH stretch spectra of (H2O)3 and benzene-(H2O)3 are primarily due to mode localization induced by the benzene molecule.
Received: 27 January 1997 / Accepted: 28 January 1997 相似文献
19.
Melchor González-Dávila J. Magdalena Santana-Casiano Frank J. Millero 《Journal of solution chemistry》2006,35(1):95-111
The oxidation rates of nanomolar levels of Fe(II) in seawater (salinity S = 36.2) by mixtures of O2 and H2O2 has been measured as a function of pH (5.8–8.4) and temperature (3–35∘C). A competition exists for the oxidation of Fe(II)
in the presence of both O2 (μ mol⋅L−1 levels) and H2O2 (nmol⋅L−1 levels). A kinetic model has been applied to explain the experimental results that considers the interactions of Fe(II) with
the major ions in seawater. In the presence of both oxidants, the hydrolyzed Fe(II) species dominate the Fe(II) oxidation
process between pH 6 and 8.5. Over pH range 6.2–7.9, the FeOH+ species are the most active, whereas above pH 7.9, the Fe(OH)02 species are the most active at the levels of CO2−3 concentration present in seawater. The predicted Fe(II) oxidation rate at [Fe(II)]0 = 30nmol⋅L−1 and pH = 8.17 in the oxygen-saturated seawater with [H2O2]0 = 50nmol⋅L−1 (log 10 k = −2.24s−1) is in excellent agreement with the experimental value of log 10 k = −2.29s−1 ([H2O2]0 = 55nmol⋅L−1, pH = 8). 相似文献
20.
以无模板生长法制备了泡沫镍载NiCo2O4纳米线正极材料, XRD和SEM表征结果表明, 所得材料为NiCo2O4纳米线, 以循环伏安法和计时电流法研究了泡沫镍载NiCo2O4纳米线对H2O2电还原的催化性能. 结果显示, 在0.4 mol/L H2O2 和 3.0 mol/L NaOH 溶液中, 当电压为-0.4 V(vs. Ag/AgCl)时, 循环伏安的电流密度达到125 mA/cm2; 当电压为-0.2, -0.3和 -0.4 V 时, 在30 min 的测试时间内, 计时电流密度几乎均为一常数, 表明以泡沫镍载NiCo2O4纳米线为催化剂电还原H2O2具有很高的活性和很好的稳定性. 相似文献