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NEW JOURNAL OF CHEMISTRY · 2020 ·Vol. 44 ·期 25 ·10300-10308 · IF 3.288

The monoiron anion fac-[Fe(CO)3I3]− and its organic aminium salts: their preparation, CO-release, and cytotoxicity

Xiuqin Yang,Jing Jin,Zhuming Guo,Zhiyin Xiao,Naiwen Chen,Xiujuan Jiang,Yi He,Xiaoming Liu

In this study, five salts containing the same anion fac-[FeII(CO)3I3]− were prepared through the reaction of cis-[Fe(CO)4I2] with organic amines whose protonated forms, i.e., (EtNH3+), (PrNH3+), (BuNH3+), (PentNH3+), and (Et2NH2+), become the cations of the salts 1, 2, 3, 4, and 5, respectively. These aminium salts, which are soluble in water and polar organic solvents such as DMSO and methanol, were characterized by various techniques including X-ray single-crystal diffraction. These salts underwent solvolysis in both water and DMSO to release CO, following first-order kinetics. In DMSO, the decomposition of these salts proceeded via a significantly simpler mechanism without the involvement of radicals than that in water, and the CO-release rate of these salts was almost linearly related to the hydrophobicity (the logarithm of the oil/water partition coefficient P) of the amines. The CO-release rate was substantially faster in water and in addition to undergoing solvolysis, the anions generated an iodine radical, I˙. Due to the complicated decomposition of these salts in water, the CO-release proceeded in a two-stage manner. The iodine radical was found to be at least partly responsible for the cytotoxicity of these salts in water; this indicates that the proposed anion has potential for applications in cancer therapy.

研究领域: 无机化学 · 药物化学 · 生物化学
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INORGANICA CHIMICA ACTA · 2017 · IF 2.002

Electrochemically probing the correlation between photo-induced CO-releasing behaviours and their LUMO energies of three diiron carbonyl complexes

Xiujuan Jiang,Hailong Wang,Yonggang Feng,Erxing Gu,Xiaoming Liu

Three diiron carbonyl complexes with different carbonyl ligands have been synthesized. Pentacarbonyl and tetracarbonyl complexes 2 and 3 were prepared by the substitution of the bound CO of complex 1 by PPh 3 . The photo-induced CO-releasing behaviours of these complexes correlate linearly to their reduction potentials and further to the energy level of their LUMOs. The more negative the reduction potentials, the more reactive the complexes. The photo-induced CO-release can be further promoted when a nucleophile is presented such as thiopronin.

研究领域: 化学 · 生物无机化学
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DALTON TRANSACTIONS · 2014 ·Vol. 43 ·期 26 ·9968-9975 · IF 4.097

Diiron hexacarbonyl complexes as potential CO-RMs: CO-releasing initiated by a substitution reaction with cysteamine and structural correlation to the bridging linkage

Xiujuan Jiang,Li Long,Hailong Wang,Limei Chen,Xiaoming Liu

The CO-releasing behaviours of nine diiron carbonyl complexes (1–9) were examined via the substitution reaction of cysteamine (CysA), of which complex 4 was reported recently. These complexes fall into three categories, the diiron core bridged by two thiolates, a dithiolate and 1,8-naphthalene dithiolate. Our results reveal that the CO-releasing rates of these complexes are highly dependent on their structures. Complexes (2–4) bearing two monothiolates as their bridging linkage (“open” form) are more vulnerable to decomposition upon nucleophilic substitution reactions compared with complexes (6–9) that possess a dithiolate as their bridging linkage. When the bridging linkage lacks an electron-donating group (complex 1), the metal centre is less negatively charged as revealed by DFT calculation, and thus it exhibits fast substitution reaction with CysA to release CO. A linkage with conjugating nature (5) shows a similar effect because electron density on the metal centre decreases due to electron-density diverting from the metal centre into the naphthalene moiety. Kinetic analysis suggests that CO-releasing at the first stage of these complexes is a first-order reaction.

研究领域: 化学 · 医学 · 材料科学
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JOURNAL OF NANOBIOTECHNOLOGY · 2019 ·Vol. 17 ·期 1 ·1-12 · IF 5.345

Programmed ROS/CO-releasing nanomedicine for synergetic chemodynamic-gas therapy of cancer

Zhao Bin,Zhao Penghe,Jin Zhaokui,Fan Mingjian,Meng Jin,He Qianjun

Background To improve the outcome of cancer treatment, the combination of multiple therapy models has proved to be effective and promising. Gas therapy (GT) and chemodynamic therapy (CDT), mainly targeting the mitochondrion and nucleus, respectively, are two emerging strategy for anti-cancer. The development of novel nanomedicine for integrating these new therapy models is greatly significant and highly desired. Methods A new nanomedicine is programmed by successive encapsulation of MnO 2 nanoparticles and iron carbonyl (FeCO) into mesoporous silica nanoparticle. By decoding the nanomedicine, acidity in the lysosome drives MnO 2 to generate ROS, ·OH among which further triggers the decomposition of FeCO into CO, realizing the effective combination of chemodynamic therapy with gas therapy for the first time. Results Acidity in the TEM drives MnO 2 to generate ROS, ∙OH among which further triggers the decomposition of FeCO into CO, realizing the effective combination of CDT and CDGT. The co-released ROS and CO do damage to DNA and mitochondria of various cancer cells, respectively. The mitochondrial damage can effectively cut off the ATP source required for DNA repair, causing a synergetic anti-cancer effect in vitro and in vivo. Conclusions The combination of CDT and CDGT causing a synergetic anti-cancer effect in vitro and in vivo. The proposed therapy concept and nanomedicine designing strategy might open a new window for engineering high-performance anti-cancer nanomedicine.

CAS / MDL: 75-09-2
研究领域: 纳米技术 · 癌症治疗 · 材料科学 · 生物医学工程
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Coatings · 2024 ·Vol. 14 ·期 11 ·1418 · IF 2.9

Construction of a Carbon Monoxide-Releasing Bioactive Hydrogel Coating on the Magnesium Alloy Surface for Better Corrosion Resistance, Anticoagulant Properties, and Endothelial Cell Growth

Renwei Gao,Lingjie Meng,Changjiang Pan

In this study, we first fabricated a crosslinked hydrogel coating by polymerizing methacryloyloxyethyl sulfonyl betaine and acrylamide (SBMA) on the magnesium (Mg) alloy surface employing ultraviolet (UV) polymerization. Bivalirudin and CO-releasing molecules (CORM-401) were further grafted onto the hydrogel coating surface to acquire a multifunctional biocompatible coating capable of releasing CO to augment corrosion-resisting properties and biocompatibility. The findings verified that the bioactive hydrogel coating significantly increased the corrosion potential and reduced the corrosion current, thereby improving the anticorrosion performance. Meanwhile, owing to the excellent hydrophilicity, the antifouling performance of the hydrogel coating, and the excellent anticoagulant performance of bivalirudin, the hydrogel coating significantly reduced the fibrinogen adsorption, platelet adhesion and activation, and hemolysis occurrence, displaying excellent ability to inhibit blood clotting. Moreover, endothelial cell (EC) experimental results demonstrated that the hydrogel coating could significantly promote EC growth, displaying great potential to induce re-endothelialization after implantation. Specifically, in the presence of cysteine capable of catalyzing CO release, the anticoagulant performance and ability to promote EC growth were further improved significantly. Therefore, the study offers an effective strategy to prepare a hydrogel coating capable of releasing CO to improve the corrosion-resisting performance and biocompatibility of Mg alloys, which is anticipated to be applied in the surface modification of Mg alloy intravascular stents.

研究领域: 材料科学 · 生物医学工程 · 表面化学 · 组织工程
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