Theoretical Investigation of the Controlled Metathesis Reactions of Methylruthenium(II) Complexes with Terminal Acetylenes

Liu, Yuxia; Chen, Guang; Wang, Hongliang; Bi, Siwei; Zhang, Dongju

doi:10.1002/ejic.201400123

Cited by 7 publications

(1 citation statement)

References 59 publications

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“…These results confirmed that the probe underwent a nucleophilic addition reaction with analyte. To validate the noncoplanar structure and the electronic behavior, we calculated the molecular structure with density functional theory (DFT). − The molecule FHMI had a large planar conjugated structure in which the hydroxyl oxygen (donor), the ketonic oxygen (acceptor-2) as well as the positive nitrogen (acceptor-1) were included. When sensing HSO 3 – , FHMI was transformed to the product HHMI, forming a saturated hydroxyl oxygen.…”

Section: Results and Discussionmentioning

confidence: 99%

Rationally Optimized Fluorescent Probe for Imaging Mitochondrial SO₂ in HeLa Cells and Zebrafish

et al. 2018

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Organisms have built up immunological systems, where mitochondrial SO 2 plays conflicting roles in regulating cell apoptosis. However, no exploration on the influence and regulating principle of mitochondrial SO 2 to the specific apoptosis type can be found, which brings about a challenge to fluorescent probes. Herein, we optimize the fluorophore and develop a new fluorescent probe FHMI ((E)-4-(3-formyl-4-hydroxystyryl)-1-methylpyridin-1-iumiodide) by equipping an ICT (intramolecular charge transfer) fluorophore HMII ((E)-4-(4-hydroxystyryl)-1-methylpyridin-1-ium iodide) with an aldehyde group that serves as both fluorescence quencher and reporting group. After the optimization, although the nonconjugated electron donor is formed when sensing SO 2 , the preset ICT fluorophore HMII is permitted to release the fluorescence at the enlarged wavelength. Compared with the traditional design, the probe FHMI exhibits obvious enhanced fluorescence with large red shift. FHMI is successfully applied to the mechanistic exploration of the dichotomous effects of mitochondrial SO 2 to cells apoptosis, showing that mitochondrial SO 2 regulates the early apoptosis of HeLa cells via the reduction of mitochondrial membrane potential. FHMI is applied to explore the dichotomous bioinfluence of mitochondrial SO 2 to HeLa cells under oxidative stress, visualizing the regulative role of mitochondrial SO 2 in the apoptotic process. For the first time, the mitochondrial SO 2 is visually found to be closely associated with the early apoptosis of HeLa cells. Moreover, FHMI proves to be readily applicable to monitoring endogenous SO 2 in zebrafish. This probe can act as an effective optical tool for exploring SO 2 in biospecimen.

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Section: Results and Discussionmentioning

confidence: 99%

Rationally Optimized Fluorescent Probe for Imaging Mitochondrial SO₂ in HeLa Cells and Zebrafish

et al. 2018

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Mononuclear or Dinuclear? Mechanistic Study of the Zinc‐Catalyzed Oxidative Coupling of Aldehydes and Acetylenes

Yue

Bai

et al. 2017

Chemistry A European J

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Although zinc catalysis is widely used in organic synthesis, very few studies on the dinuclear zinc mechanism have been reported. Here, a dinuclear zinc pathway is proposed for the Zn(OTf) -catalyzed oxidative coupling of aldehydes with terminal alkynes. DFT calculations revealed that the deprotonation of the terminal alkyne would preferentially lead to the formation of a dinuclear zinc intermediate. The nucleophilic addition of this intermediate to an aldehyde, followed by an Oppenauer-type oxidation was investigated theoretically according to the mono- and dinuclear pathways. The formation of a dinuclear zinc intermediate from a mononuclear alkynyl zinc complex was exergonic, favoring the dinuclear zinc pathway. The subsequent protonation and regeneration of the active dinuclear catalyst were also evaluated by DFT calculations. The oxidizabilities of various aldehydes and ketones were evaluated to determine the best oxidant for this step. Trifluoroacetaldehyde was predicted to be a better oxidant for this reaction because its calculated energy barrier for the Oppenauer-type oxidation step was much lower than that of the other carbonyl complexes.

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A novel dual-ratiometric-response fluorescent probe for SO2/ClO− detection in cells and in vivo and its application in exploring the dichotomous role of SO2 under the ClO− induced oxidative stress

et al. 2017

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Intracellular reactive sulfur species and reactive oxygen species play vital roles in immunologic mechanism. As an emerging signal transmitter, SO can be generated as the anti-oxidant, while SO is also a potential oxidative stress-inducer in organism. Aiming to elucidate in-depth the dichotomous role of SO under oxidative stress, we designed a dual-response fluorescent probe that enabled the respective or successive detection of SO and ClO. The probe itself emits the red fluorescence (625 nm) which can largely switch to blue (410 nm) and green fluorescence (500 nm) respectively in response to SO and ClO, allowing the highly selective and accurate ratiometric quantification for both SO and ClO in cells. Moreover the ultrafast (SO: <60 s; ClO: within sec) and highly sensitive (detection limits: SO: 3.5 nM; ClO: 12.5 nM) detection were achieved. With the robust applicability, the developed probe was successfully used to quantify SO and endogenous ClO in respectively the HeLa cells and the RAW 264.7 cells, as well as to visualize the dynamic of SO/ClO in zebrafish. The fluorescent imaging studies and flow cytometry analysis confirmed the burst-and-depletion and meanwhile the oxidative-and-antioxidative effects of intracellular SO under the NaClO induced oxidative stress.

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Theoretical Investigation of the Controlled Metathesis Reactions of Methylruthenium(II) Complexes with Terminal Acetylenes

Cited by 7 publications

References 59 publications

Rationally Optimized Fluorescent Probe for Imaging Mitochondrial SO₂ in HeLa Cells and Zebrafish

Rationally Optimized Fluorescent Probe for Imaging Mitochondrial SO₂ in HeLa Cells and Zebrafish

Mononuclear or Dinuclear? Mechanistic Study of the Zinc‐Catalyzed Oxidative Coupling of Aldehydes and Acetylenes

A novel dual-ratiometric-response fluorescent probe for SO2/ClO− detection in cells and in vivo and its application in exploring the dichotomous role of SO2 under the ClO− induced oxidative stress

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Theoretical Investigation of the Controlled Metathesis Reactions of Methylruthenium(II) Complexes with Terminal Acetylenes

Cited by 7 publications

References 59 publications

Rationally Optimized Fluorescent Probe for Imaging Mitochondrial SO2 in HeLa Cells and Zebrafish

Rationally Optimized Fluorescent Probe for Imaging Mitochondrial SO2 in HeLa Cells and Zebrafish

Mononuclear or Dinuclear? Mechanistic Study of the Zinc‐Catalyzed Oxidative Coupling of Aldehydes and Acetylenes

A novel dual-ratiometric-response fluorescent probe for SO2/ClO− detection in cells and in vivo and its application in exploring the dichotomous role of SO2 under the ClO− induced oxidative stress

Contact Info

Product

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Rationally Optimized Fluorescent Probe for Imaging Mitochondrial SO₂ in HeLa Cells and Zebrafish

Rationally Optimized Fluorescent Probe for Imaging Mitochondrial SO₂ in HeLa Cells and Zebrafish