1118-67-8Relevant articles and documents
Metal-Anion Coordination and Linker-Anion Hydrogen Bonding in the Construction of Metal-Organic Frameworks from Bipyrazole
Zhang, Erpan,Jia, Qizhang,Zhang, Jun,Ji, Zhenguo
, p. 191 - 195 (2016)
Two new two-dimensional frameworks based on packing of square grids, Cu(Me4bpz)2(NO3)2 (1) and Zn(Me4bpz)(SO4) (2) (Me4bpz=3,3′,5,5′-tetramethyl-4,4′-bipyrazole), have been synthesized by mild solvothermal method. In addition to the major metal-organic linker coordination, they allow us to study how the metal-inorganic anion coordination and organic linker-inorganic anion hydrogen bonding affect the resulting structures during the framework assembly. Two new MOFs based on bipyrazole were synthesized, and they provide examples of metal-anion coordination and linker-anion hydrogen bonding during the framework assembly.
A soluble bis-chelated gold(I) diphosphine compound with strong anticancer activity and low toxicity
Wang, Yanli,Liu, Minyu,Cao, Ran,Zhang, Wanbin,Yin, Ming,Xiao, Xuhua,Liu, Quanhai,Huang, Niu
, p. 1455 - 1466 (2013)
Gold-containing compounds have shown anticancer potential, but their clinical applications have been severely limited by poor stability and high toxicity in vivo. Here, we report a novel soluble bis-chelated gold(I)-diphosphine compound (GC20) with strong anticancer activity and low toxicity. GC20 shows strong antiproliferation potency against a broad spectrum of cancer cell lines including cisplatin-resistant cancer cells (IC50 ≈ 0.5 μM) and significantly reduces tumor growth in several tumor xenografts in mouse models at doses as low as 2 mg/kg. Studies of its mechanism revealed that GC20 specifically inhibits the enzymatic activity of thioredoxin reductase by binding to selenocysteine residue, without targeting other well-known selenol and thiol groups contained in biomolecules. Remarkably, in animal studies GC20 was shown to be well tolerated even at the high dose of 8 mg/kg. Our results strongly suggest that GC20 represents a promising candidate for the development of novel anticancer drugs.
Bioinspired models for an unusual 3-histidine motif of diketone dioxygenase enzyme
Ramasubramanian, Ramamoorthy,Anandababu, Karunanithi,M?sch-Zanetti, Nadia C.,Belaj, Ferdinand,Mayilmurugan, Ramasamy
, p. 14326 - 14336 (2019)
Bioinspired models for contrasting the electronic nature of neutral tris-histidine with the anionic 2-histidine-1-carboxylate facial motif and their subsequent impact on catalysis are reported. Herewith, iron(ii) complexes [Fe(L)(CH3CN)3](SO3CF3)21-3 of tris(2-pyridyl)-based ligands (L) have been synthesized and characterized as accurate structural models for the neutral 3-histidine triad of the enzyme diketone dioxygenase (DKDO). The molecular structure of one of the complexes exhibits octahedral coordination geometry and Fe-N11py bond lengths [1.952(4) to 1.959(4) ?] close to the Fe-NHis bond distances (1.98 ?) of the 3-His triad in the resting state of the enzyme, as obtained by EXAFS studies. The diketonate substrate-adduct complexes [Fe(L)(acacR)](SO3CF3) (R = Me, Ph) of 1-3 have been obtained using Na(acacR) in acetonitrile. The Fe2+/3+ redox potentials of the complexes (1.05 to 1.2 V vs. Fc/Fc+) and their substrate adducts (1.02 to 1.19 V vs. Fc/Fc+) appeared at almost the same redox barrier. All diketonate adducts exhibit two Fe(ii) → acac MLCT bands around 338 to 348 and 430 to 490 nm. Exposure of these adducts to O2 results in the decay of both MLCT bands with a rate of (kO2) 5.37 to 9.41 × 10-3 M-1 s-1. The kO2 values were concomitantly accelerated 20 to 50 fold by the addition of H+ (acetic acid), which nicely models the rate enhancement in the enzyme kinetics by the glutamate residue (Glu98). The oxygenation of the phenyl-substituted adducts yielded benzoin and benzoic acid (40% to 71%) as cleavage products in the presence of H+ ions. Isotope-labeling experiments using 18O2 showed 47% incorporation of 18O in benzoic acid, which reveals that the oxygen originates from dioxygen. Thus, the present model complexes exhibit very similar chemical surroundings to the active site of DKDO and mimic its functions elegantly. On the basis of these results, the C-C bond cleavage reaction mechanism is discussed.
An efficient and stereoselective approach to 14-membered hexaaza macrocycles using novel semicarbazone-based amidoalkylation reagents
Fesenko, Anastasia A.,Yankov, Alexander N.,Shutalev, Anatoly D.
, p. 5784 - 5787 (2016)
An efficient synthesis of hydrazones of 4-(3-oxobutyl)semicarbazides and 4-(3-oxobutyl)semicarbazones using novel semicarbazone-based amidoalkylation reagents, 1-arylidene-4-[(aryl)(tosyl)methyl]semicarbazides, has been developed. The synthesis involved reaction of the latter with the Na-enolate of acetylacetone, followed by a base-promoted retro-Claisen reaction and treatment of the obtained 4-(3-oxobutyl)semicarbazones with hydrazine or methylhydrazine. The prepared hydrazones were converted stereoselectively into 14-membered cyclic bis-semicarbazones under acidic conditions. Especially high selectivity (trans/cis ? 97:3) was observed upon the macrocyclization of 4-(3-oxobutyl)semicarbazone hydrazones. A plausible reaction pathway and the stereochemistry of this cyclization were discussed.
Synthesis and characterization of Pd(II) antitumor complex, DFT calculation and DNA/BSA binding insight through the combined experimental and theoretical aspects
Feizi-Dehnayebi, Mehran,Dehghanian, Effat,Mansouri-Torshizi, Hassan
, (2021)
A novel palladium(II) complex, [Pd(bpy)(acac)]NO3 (where bpy and acac are 2,2′-bipyridine and acetylacetonato), has been synthesized and fully characterized through 1H NMR, UV-Vis and FT-IR spectra, conductivity measurement and elemental analysis. Geometry optimization using DFT calculation demonstrated that a square-planar geometry is built around Pd(II) atom. The MEP and FMO analysis were also applied. Partition coefficient evaluation was conducted to determine the lipophilicity of the compound which follows the order complex > cisplatin. The antitumor activity of the complex has been evaluated on K562 cancer cells by MTT method, which exhibited an appropriate activity in compare to cisplatin. The interaction of [Pd(bpy)(acac)]NO3 towards biomolecules (CT-DNA and BSA) was investigated through in-detail fluorescence, UV–Vis and other techniques. The findings of fluorescence titration demonstrated that the Pd(II) complex binds to CT-DNA via hydrophobic and with BSA through van der Waals forces and hydrogen bond. UV–Vis experiment revealed a reduction in the absorption spectra of biomolecules in presence of the complex. The binding affinity was further endorsed for CT-DNA utilizing viscosity measurement and gel electrophoresis and for BSA via CD spectroscopy and FRET calculation. In addition, molecular docking supports the findings of experiments and indicates that the Pd(II) complex appears to be situated at DNA intercalation position and BSA Sudlow's site I. All results have shown that this compound may be a useful potential antitumor candidate for further medical purposes.
A novel palladium(II) antitumor agent: Synthesis, characterization, DFT perspective, CT-DNA and BSA interaction studies via in-vitro and in-silico approaches
Feizi-Dehnayebi, Mehran,Dehghanian, Effat,Mansouri-Torshizi, Hassan
, (2021)
Since numerous people annually pass away due to cancer, research in this field is essential. Thus a newly made and water like palladium(II) complex of formula [Pd(phen)(acac)]NO3, where phen is 1,10-phenanthroline and acac is acetylacetonato ligand, has been synthesized by the reaction between [Pd(phen)(H2O)2](NO3)2 and sodium salt of acetylacetone in the molar ratio of 1:1. It has been structurally characterized via the methods such as conductivity measurement, elemental analysis and spectroscopic methods (FT-IR, UV–Vis and 1H NMR). The geometry optimization of this complex at the DFT level of theory reveals that Pd(II) atom is situated in a square-planar geometry. The complex has been screened for its antitumor activity against K562 cancer cells which demonstrated efficacious activity. The interaction of above palladium(II) complex with CT-DNA as a target molecule for antitumor agents and BSA as a transport protein was studies by a variety of techniques. The results of UV–Vis absorption and fluorescence emission indicated that the Pd(II) complex interacts with EB + CT-DNA through hydrophobic and with BSA by hydrogen bonding and van der Waals forces at very low concentrations. In these processes, the fluorescence quenching mechanism of both the macromolecules seems to be the combined dynamic and static. The interaction was further supported for CT-DNA by carrying out the gel electrophoresis and viscosity measurement and for BSA by the circular dichroism and F?rster resonance energy transfer experiments. Furthermore, results of partition coefficient determination showed that the [Pd(phen)(acac)]NO3 complex is more lipophilic than that of cisplatin. Moreover, molecular docking simulation confirms the obtained results from experimental tests and reveals that the complex tends to be located at the intercalation site of DNA and Sudlow's site I of BSA.
Method for synthesizing ruthenium (III) acetylacetonate (by machine translation)
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Paragraph 0011; 0025; 0033; 0035-0040; 0042-0044, (2020/09/10)
A method for synthesizing the ruthenium (III) acetylacetonate, which comprises the following steps of: a, dissolving the hydrated ruthenium trichloride in water, reacting with the base to obtain the ruthenium salt solution; b, reacting the ruthenium salt solution with the acetyl acetonate solution; b, purifying the ruthenium salt solution and the acetyl acetonate solution under heating conditions; and obtaining the total reaction equation of the ruthenium (III) chloride solution and the chloride ion content _AOMARKENCODTX0AO_ 80 - 90% 50 ppm. In the formula, HL is a strong acid of a non-coordinating anion acac is acetyl acetonate. M is Na or K; the content of impurity chloride ions is reduced while the high yield of ruthenium (III) acetylacetonate is guaranteed, the product quality is improved, and industrial production is facilitated. (by machine translation)
Oxidative Mechanochemistry: Direct, Room-Temperature, Solvent-Free Conversion of Palladium and Gold Metals into Soluble Salts and Coordination Complexes
Do, Jean-Louis,Tan, Davin,Fri??i?, Tomislav
supporting information, p. 2667 - 2671 (2018/02/06)
Noble metals are valued, critical elements whose chemical activation or recycling is challenging, and traditionally requires high temperatures, strong acids or bases, or aggressive complexation agents. By using elementary palladium and gold, demonstrated here is the use of mechanochemistry for noble-metal activation and recycling by mild, clean, solvent-free, and room-temperature chemistry. The process leads to direct, efficient, one-pot conversion of the metals, including spent catalysts, into either simple water-soluble salts or metal–organic catalysts.
Synthesis method of 3,5-dimethoxy pyrrole-2-methanoic acid
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Paragraph 0005; 0007, (2017/01/19)
The invention discloses a synthesis method of 3,5-dimethoxy pyrrole-2-methanoic acid, and belongs to the field of chemosynthesis. According to the method, firstly, ethyl acetate, acetone and absolute ether are used as raw materials; metallic sodium is added to generate 3-oxo-2-pentene-2-sodium alkoxide; then, aminomalonic acid diethyl ester is added under the conditions of glacial acetic acid and argon; 3,5-dimethoxy pyrrole-2-ethyl formate is obtained through work procedures such as backflow and suction filtering; KF is used for substitution on the methyl under the specific conditions to obtain 3,5-dimethoxy pyrrole-2-ethyl formate; then, fluoro is used for processing the 3,5-dimethoxy pyrrole-2-ethyl formate under the conditions of NaS, etherified reagents and the like; finally, hydrolysis is performed to obtain the 3,5-dimethoxy pyrrole-2-methanoic acid.
Achieving chemo-, regio-, and stereoselectivity in palladium-catalyzed reaction of γ-borylated allylic acetates
Kukkadapu, Krishna Kishore,Ouach, Aziz,Lozano, Pedro,Vaultier, Michel,Pucheault, Mathieu
supporting information; experimental part, p. 4132 - 4135 (2011/10/02)
Three-carbon highly functionalized γ-borylated allylic acetates underwent a regio- and stereocontrolled Tsuji-Trost reaction in the presence of palladium complexes. An ipso substitution of the acetate with complete stereoretention of the chiral center was achieved, leading to vinylic boronates with enantiomeric excesses above 99%.
