- Thioether sulfur-bound [Cu2] complexes showing catechol oxidase activity and DNA cleaving behaviour
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Rational ligand design approaches allowed {Cu2(μ-OH/OMe)} cores to be accommodated within μ-phenoxido bis(tetradentate) and μ-phenoxido bis(tridentate) ligands having thioether donors. The complexes [Cu2(μ-H2L1)(μ-OH)](ClO4)2·2H2O (1), [Cu2(μ-L2)(μ-OH)(OH2)](ClO4)2 (2a) and [Cu2(μ-L2)(μ-OCH3)(OH2)](ClO4)2 (2b) were obtained from an N2O3S2 donor set bearing the H3L1 ligand (2,6-bis-[{2-(2-hydroxyethylthio)ethylimino}methyl]-4-methylphenol) and N2OS2 donor set containing the HL2 ligand (4-methyl-2,6-bis-[{2-(methylthio)phenylimino}methyl]phenol) without showing double phenoxido bridging or any type of preformed inter-fragment aggregation. Previously, we showed that H3L (2,6-bis[((2-(2-hydroxyethoxy)ethyl)imino)methyl]-4-methylphenol), the ether analogue of H3L1, in the presence of carboxylate anions, was responsible for the self-aggregation of preformed {Cu2} fragments and gave two types of [Cu4] complexes comprising [Cu4O] and [Cu4(OH)2] cores (T. S. Mahapatra, A. Bauzá, D. Dutta, S. Mishra, A. Frontera and D. Ray, ChemistrySelect, 2016, 1, 64-74). The molecular structures of 1, 2a and 2b were determined via single crystal X-ray diffraction and solution studies, which indicated the presence of [Cu2] species. This was further confirmed via UV-vis spectroscopy and HRMS analysis. The synthesized complexes were screened for their potential as catalysts for the catalytic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBCH2). A change in the mechanism of catalytic oxidation was observed with a change in the ligand backbone. All three complexes also showed DNA binding properties, which were further substantiated via molecular docking studies. Their DNA binding affinities were quantitatively ascertained using their intrinsic binding constant, Kb, values which were found to be 4.2 × 104, 5.6 × 104 and 4.8 × 104 M-1, respectively. Furthermore, the complexes displayed efficient DNA cleavage behaviour with pBR322 and the oxidative path was established in presence of ROS, singlet oxygen, 1O2, and the superoxide anion, O2·-.
- Das, Manisha,Afsan, Zeenat,Basak, Dipmalya,Arjmand, Farukh,Ray, Debashis
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- Entrapment of a Pseudo-Tetrahedral CoII Center by Thioether Sulfur Bound {Co2(μ-L)} Fragments: Synthesis, Field-Induced Single-Ion Magnetism and Catechol Oxidase Mimicking Activity
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Simultaneous incorporation of both CoII and CoIII ions within a new thioether S-bearing phenol-based ligand system, H3L (2,6-bis-[{2-(2-hydroxyethylthio)ethylimino}methyl]-4-methylphenol) formed [Co5] aggregates [CoIICoIII 4L2(μ-OH)2(μ1,3-O2CCH3)2](ClO4)4?H2O (1) and [CoIICoIII 4L2(μ-OH)2(μ1,3-O2CC2H5)2](ClO4)4?H2O (2). The magnetic studies revealed axial zero-field splitting (ZFS) parameter, D/hc=?23.6 and ?24.3 cm?1, and E/D=0.03 and 0.00, respectively for 1 and 2. Dynamic magnetic data confirmed the complexes as SIMs with Ueff/kB=30 K (1) and 33 K (2), and τ0=9.1×10?8 s (1), and 4.3×10?8 s (2). The larger atomic radius of S compared to N gave rise to less variation in the distortion of tetrahedral geometry around central CoII centers, thus affecting the D and Ueff/kB values. Theoretical studies also support the experimental findings and reveal the origin of the anisotropy parameters. In solutions, both 1 and 2 which produce {CoIII 2(μ-L)} units, display solvent-dependent catechol oxidation behavior toward 3,5-di-tert-butylcatechol in air. The presence of an adjacent CoIII ion tends to assist the electron transfer from the substrate to the metal ion center, enhancing the catalytic oxidation rate.
- Das, Manisha,Basak, Dipmalya,Trávní?ek, Zdeněk,Van?o, Ján,Ray, Debashis
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p. 3898 - 3914
(2019/11/11)
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- Synthetic method of intermediate 2-amino-2-hydroxyl-diethyl sulfide
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The invention discloses a synthetic method of intermediate 2-amino-2-hydroxyl-diethyl sulfide. According to the synthetic method of intermediate 2-amino-2-hydroxyl-diethyl sulfide, beta-mercaptoethanol, sodium hydroxide, 2-Chloroethylaminehydrochloride, FeCl3.6H2O, and CH3COONa.3H2O are taken as the main raw materials; beta-mercaptoethanol is reacted wtih 2-Chloroethylaminehydrochloride so as to obtain straight chain thioether compound 2-amino-2-hydroxyl-diethyl sulfide. A catalyst micro nano structure formation process comprises a rapid amorphous particle nucleation process and a subsequent low speed particle agglomeration and preferred orientation growth process; in a surfactant free solvothermal process, glycol is taken as a chelating ligand, a reducing agent, and a high boiling solvent. The synthetic method is capable of solving waste liquid generation and discharging problems, and product yield is increased under an optimized raw material ratio.
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Paragraph 0008; 0009; 0010; 0011; 0012; 0013; 0014-0029
(2018/09/08)
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- Has high water washing fastness and bears the friction fastness reactive red dye and the preparation method
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The invention discloses a reactive red dye with high washing fastness and rubbing fastness and a preparation method of the reactive red dye. Acetanilide reacts with chlorosulfonic acid and sulfoxide chloride to generate acetylsulfanilyl chloride; acetylsulfanilyl chloride is condensed with a sulfide generate by reacting a 2-chlorethamin hydrochloride with mercaptoethanol to obtain thioether; the thioether is oxidized and esterified to obtain 2-[2-(4-aminobenzenesulfonamido) ethyl sulfuryl] hydroxyethyl sulfate which is primarily condensed with cyanuric chloride and secondarily condensed with H acid to obtain a condensation compound; the condensation compound is cooled and then coupled with the diazonium salt of 1.5 acid under an alkaline condition, and the product is filtered and then the filtrate is collected and is subjected to direct spray drying to obtain a semi-finished product. The reactive red dye has the characteristics of bright color, high solubility high substantivity, high compatibility, high lifting power, high fixation rate, excellent diversified fastness and the like. The reactive red dye is suitable for dyeing, printing and pad dyeing of cellulosic fibers, protein fibers, viscose and polyarmide fibers, and higher than common types in rubbing fastness and washing fastness by 0.5 to 1 level.
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Paragraph 0049; 0050; 0067
(2018/03/01)
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- Active benzene sulfonamide ethyl sulphone base hydroxy ethyl sulfate aniline compounds of preparation method (by machine translation)
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The invention discloses a benzene sulfonamide ethyl sulphone base hydroxy ethyl sulfate aniline compound and its preparation method, acetyl aniline with chlorosulfuric acid, thionyl chloride reaction generating P-acetyl amino sulfonyl chloride, with 2 - chloroethylamine hydrochloride and mercapto ethanol produced by the reaction of sulfide condensation shall thioether, the thioether re-oxidation, esterification or sulfonated to obtain 2 - [2 - (4 - amino sulfuryl amidogen) sulfuryl] hydroxy ethyl sulfate or 2 - [2 - (4 - amino sulfuryl amidogen) sulfuryl] hydroxy ethyl sulfate - 3 - sulfonic acid. The active benzene sulfonamide ethyl sulphone base hydroxy ethyl sulfate aniline compound with 4 - (2 - hydroxyethyl sulphone sulfate) compared with the aniline; synthesis of the reactive dye has a bright, low substantivity, uptake, fixation is relatively high, the hydrolysis of the dye is little, and the like excellent fastness, especially light fastness, high color fastness resistance, friction-resistant fastness is higher than the common varieties of 0.5 - 1 level. (by machine translation)
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Paragraph 0044; 0047; 0048
(2018/05/16)
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- A novel reactive blue dye and its preparation method
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The invention discloses a novel reactive blue dye and a preparation method of the novel reactive blue dye. The preparation method of the compound comprises the following steps: performing condensation on cyanuric chloride and 2-[2-(4-aminobenzenesul fonamide) ethyl sulfuryl] ethoxyl-sulphating compound and then performing secondary condensation on an obtained condensation compound and 2,4-diaminobenzenesulfonic acid; reducing the temperature of the condensate and performing diazotization; performing acid coupling on the condensate and H acid; then performing alkali coupling on the condensate and diazonium salt of sodium sulfamate or 2,5-disulfonic acid-phenylamine; spraying and drying to obtain a semi-finished product. The reactive blue dye has the characteristics of bright and deep color, high dissoluvability, high compatibility, high elevating power, high fixation rate, high firmness degree of all items and the like; the dye is suitable for coloring, printing and pad-dyeing of cellulosic fibers, protein fibers, viscose fibers and polyamide, and the color fasteness to sunlight and the fastness to rubbing of the novel reactive blue dye are 0.5-1 grade more than those of the general varieties.
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Paragraph 0018; 0047; 0050-0051
(2018/01/11)
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- A new kind of very deep reactive orange or yellow dye and its preparation method
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The invention discloses a novel ultradeep reactive orange or yellow dye and a preparation method thereof. The preparation method comprises the following steps: carrying out tertiary coupling on 3,5-diamido-benzoic acid and 4-methyl-2-sulfo-aniline (or derivatives), 2-[2-(4-aminophenylsulfamido)ethylsulfuryl]hydroxyethyl sulfate, 2-[2-(4-aminophenylformamido)ethylsulfuryl]hydroxyethyl sulfate or diazonium salt of 2-methoxy- or 2-methyl- or 2-chloro- or 2-hydro- or 2-sulfo-4-(beta-hydroxyethylsulfurylsulfate)aniline, filtering, collecting the filtrate, and directly carrying out spray drying to obtain the semifinished product. The novel ultradeep reactive orange or yellow dye has the characteristics of bright color, deep color, high solubility, especially high compatibility with black, high lifting power, high fixation rate, favorable fastness and the like. The novel ultradeep reactive orange or yellow dye is suitable for dyeing, printing and pad dyeing of cellulose fibers, protein fibers, viscose fibers and polyamide fibers, has higher fastness to rubbing than common varieties by Grade 0.5-1, and has low nylon staining strength.
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Paragraph 0042; 0045; 0046; 0077; 0080; 0081
(2018/01/11)
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- Chemoimmunotherapy of cancer
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The preparation of a series of water-soluble mustard haptens for chemoimmunotherapy of cancer is described. Preliminary screening data are given, indicating some activity against P388 lymphocytkc leukemia for those compounds containing the most potent immunogenic functional groups.
- Soloway,Wright,Subramanyam,Gozzo
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p. 1357 - 1362
(2007/10/05)
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