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1.
Multidrug resistance (MDR) in cancer is one of the major obstacles of chemotherapy. We have recently identified a series of 8-hydroxyquinoline Mannich base derivatives with MDR-selective toxicity, however with limited solubility. In this work, a novel 5-nitro-8-hydroxyquinoline-proline hybrid and its Rh(η5-C5Me5) and Ru(η6-p-cymene) complexes with excellent aqueous solubility were developed, characterized, and tested against sensitive and MDR cells. Complex formation of the ligand with essential metal ions was also investigated using UV-visible, circular dichroism, 1H NMR (Zn(II)), and electron paramagnetic resonance (Cu(II)) spectroscopic methods. Formation of mono and bis complexes was found in all cases with versatile coordination modes, while tris complexes were also formed with Fe(II) and Fe(III) ions, revealing the metal binding affinity of the ligand at pH 7.4: Cu(II) > Zn(II) > Fe(II) > Fe(III). The ligand and its Rh(III) complex displayed enhanced cytotoxicity against the resistant MES-SA/Dx5 and Colo320 human cancer cell lines compared to their chemosensitive counterparts. Both organometallic complexes possess high stability in solution, however the Ru(II) complex has lower chloride ion affinity and slower ligand exchange processes, along with the readiness to lose the arene ring that is likely connected to its inactivity.  相似文献   

2.
Multiferroic (MF) composites based on nanoparticles consisting of a silica core and a shell of spin-variable Fe(III) complexes in a polymer matrix (polystyrene) were synthesized and characterized by different methods. The nanoparticles had the formula 80SiO2·20{Fe[OSi(Me)(OEt)2]3}, and their particle size was on the order of 5–7 nm. Dielectric and electron spin resonance studies showed the presence of two types of Fe ions in the nanocomposite. Iron ions in the low-spin state [Fe(III)-LS] and iron ions in the high-spin state [Fe(III)-HS], which were bound by indirect exchange interactions through oxygen and silicon atoms {[Fe(III)-LS]─O─Si─O─[Fe(III)-HS]} were responsible for the MF properties of the composites with core–shell nanoparticles. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47681.  相似文献   

3.
A set of six new polystyrene anchored metal complexes have been synthesized by the reaction of the metal salt with the polystyrene anchored Schiff base of vanillin. These complexes were characterized by elemental analyses, Fourier transform infrared spectroscopy, diffuse reflectance studies, thermal studies, and magnetic susceptibility measurements. The elemental analyses suggest a metal : ligand ratio of 1 : 2. The ligand is unidentate and coordinates through the azomethine nitrogen. The Mn(II), Fe(III), Co(II), Ni(II), and Cu(II) complexes are all paramagnetic while Zn(II) is diamagnetic. The Cu(II) complex is assigned a square planar structure, while Zn(II) is assigned a tetrahedral structure and Mn(II), Fe(III), Co(II), and Ni(II) are all assigned octahedral geometry. The thermal analyses were done on the ligand and its complexes to reveal their stability. Further, the application of the Schiff base as a chelating resin in ion removal studies was investigated. The polystyrene anchored Schiff base gave 96% efficiency in the removal of Ni(II) from a 20‐ppm solution in 15 min, without any interference from ions such as Mn(II), Co(II), Fe(III), Cu(II), Zn(II), U(VI), Na+, K+, NH4+, Ca2+, Cl?, Br?, NO3?, NO2?,and CH3CO2?. The major advantage is that the removal is achieved without altering the pH. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1536–1539, 2005  相似文献   

4.
The structure of the bromate-oxidized wheat starch (OS) contains partly opened glucose units with carbonyl and carboxyl groups at C2-, C3- or C6-positions. OS with a variable degree of oxidation (DO) was studied in alkaline conditions as a water-soluble complexing agent for Fe(III), Cu(II), Ni(II) and Zn(II) ions, which are common in various wastewaters. Complexation was studied by inductively coupled plasma-optical emission spectrometry (ICP–OES) in a single metal ion or multi-metal ion solutions. The DO affected the efficiency of the complexation with metal ions. OS with the high DO (carboxyl and carbonyl DO of 0.72 and 0.23, respectively) complexed and held Fe(III) or Zn(II) ions in a soluble form effectively in 0.5 mM single ion alkaline solution with the molar ratio of 0.65:1 of oxidized starch-to-metal ion (OS-to-M). The OS-to-M molar ratio of 1.3:1 was required to form a soluble complex with Cu(II) or Ni(II) ions. These complexes were thermally stable at the temperature range of 20–60 °C. OS with the low DO (carboxyl and carbonyl DO 0.47 and 0.17, respectively) complexed Zn(II) ions highly, Cu(II) and Ni(II) ions poorly and Fe(III) ions only partly. In the multi-metal ion solution of OS the solubility of these metal ions improved with the increasing DO of starch, which followed the same tendency as was observed in the single metal ion systems. The increased molar ratio of OS-to-M improved the complexation and solubility of the metal ions in all multi-metal ion series. As the soluble multi-metal ion complexes were reanalyzed after 7 days, all solutions had kept the high complexation and solubility of metal ions (ca. 90%). Complexation by OS did not show a selective binding of the ions in the multi-metal ion solution. It was concluded that the flexible, opened ring structure units of OS prevented the selective binding to metal ions but made the complexes highly stable. Titrimetric studies of OS–Fe(III) complexation showed that each anhydroglucose unit of OS had more than one coordination site and as the content of OS increased, the free sites coordinated to Fe(III) ions and formed cross-linked starch structures.  相似文献   

5.
Absorptive properties of nitric oxide by Fe(II)—aminocarboxylic acid complexes have been investigated, and the compositions of the Fe(II)NO—chelate complexes in solution determined by the electrochemical and spectroscopic methods. Fe(II)—EDTA forms the 1:2 complex (Fe(II) (NO)2EDTA) with nitric oxide, —G and—EDDA the 1:1 complexes, and—NTA and—IDA both of the 1:1 and 1:2 complexes. The abilities of the Fe(II)—chelate complexes to absorb nitric oxide decreased in the order Fe(II)—EDTA > —NTA > —IDA > —G > —EDDA, which is in agreement with that of a decrease of its stability constant.  相似文献   

6.
Electroactive 2,2′: 6,2″-terpyridinyl ligands ( 3, 5, 6 ) and their iron(II) ( 7a–9a ) and ruthenium(II) complexes ( 7b–9b ) were synthesized. Bis[3-(aminophenyl)-2,2′ :6,2″-terpyridinyl]metal(II) complexes ( 7a, 7b ) and bis[2-(hydroxyphenyl)-2,2′ :6,2″-terpyridinyl]metal(II) complexes ( 8a, 8b ) were electropolymerized on to the surface of Pt or In-SnO2 (ITO) electrodes in acetonitrile containing Bu4NCIO4 by scanning the potential between O and + 1.6V (for 7a and 7b ), and ?0.8 and +1.6V (for 8a and 8b ) versus saturated calomel electrode. The electrodes obtained by electropolymerization exhibited reversible electrochromism based on Fe(II)/Fe(III) or Ru(II)/Ru(III) redox couple. Photoresponses to visible light were found in the modified electrode obtained by electropolymerization of ruthenium complex 7b in an aqueous LiClO4 solution containing methylviologen (cation MV2+) under an O2 atmosphere. The mechanism for the photoresponded cathodic current was explained in terms of an excitation of bis(terpyridinyl)ruthenium(II) complex [Ru(terpy)22+] by visible light, an electron transfer from the excited state [Ru(terpy)2+*2] to MV2+, reduction of Ru(terpy)3+2 at an electrode, and oxidation of MV+* with O2.  相似文献   

7.
The metal‐ion complexation behavior and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid) were investigated. The polymeric ligand was prepared by solution polymerization. The metal‐ion complexation was studied with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) ions. The metal uptake followed the order: Cu(II) > Cr(III) > Mn(II) > Co(II) > Fe(III) > Zn(II) > Ni(II). The polymeric ligand and the metal complexes were characterized by various spectral methods. The catalytic activity of the metal complexes were investigated toward the hydrolysis of p‐nitrophenyl acetate (NPA). The Co(II) complexes exhibited high catalytic activity. The kinetics of catalysis was first order. The hydrolysis was controlled by pH, time, amount of catalyst, and temperature. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 272–279, 2004  相似文献   

8.
The reactions between Fe3+ ions and acetylacetonedioxime (AADO) have been studied by potentiometric, polarographic and spectrophotometric methods. Two Fe3+ ions are reduced in aqueous solution by one AADO molecule to give Fe2+ ions and the oxidized form of AADO (NPO = AADO-2e = 2-nitrosopent-2-en-4-one oxime). NPO forms a water soluble, red coloured complex with Fe (III). The synthesis of bis (2-nitrosopent-2-en-4-one oximato) Fe (III) complex is described. The elemental analysis of the solid complex is consistent with the composition FeO (NPO)2 (OH). The IR, EPR and Mössbauer spectra of the complex are presented and the bonding properties of the coordination environment of Fe (III) is discussed. A mechanism for the oxydoreduction and complexation reactions for the Fe3+ -AADO system is proposed and its kinetic parameters are: kox.red. = 1.72 × 10 ?1 min?1, kcompl. = 5.13 l0?2min?1.  相似文献   

9.
A novel cyano-bridged Sr(II)–Fe(III) polymeric complex ([Sr3(phen)6(H2O)6{Fe(CN)6}2]·phen·6.5H2O)n (1) has been synthesized and structurally characterized. The complex contains alternating octanuclear 24-membered and tetranuclear 12-membered metallocycles, which are repeated to form a polymeric chain. The Sr(II) centres are eight coordinated with distorted bicapped trigonal prismatic geometry while the Fe(III) centres have six coordinate octahedral geometry.  相似文献   

10.
Conventional precipitation methods of industrial sewage and wastewater purification are not very effective and are insufficient in many cases. This implies the necessity of searching new, effective methods exploiting cheap, accessible and ecologically safe ion exchangers and sorbents. The paper presents the studies on removal of heavy metal ions — Cu(II), Zn(II), Co(II), Ni(II) and Fe(III) — from aqueous solutions in the presence of EDTA carried out on commercially available, strongly basic monodisperse anion exchangers with the polystyrene skeleton gel, Lewatit MonoPlus M 500; and the macroporous, Lewatit MonoPlus MP 500, which are more widely applied in water purification processes. The research results indicate a high affinity of the Lewatit MonoPlus M 500 and Lewatit MonoPlus MP 500 anion exchangers in the chloride form for copper(II), nickel(II), cobalt(II) and zinc(II) complexes with EDTA. The affinity series for the heavy metal complexes in the 0.001 M M(II)/(III)–0.001 M EDTA and 0.001 M M(II)/(III)–0.001M EDTA–0.001 M–0.002 M NaOH systems were found for the Lewatit MonoPlus M 500 anion exchanger in the chloride form to be as follows: Cu(II) > Ni(II) > Co(II) > Zn(II) Fe(III). In the case of the Lewatit MonoPlus MP 500 anion exchanger in the chloride form there was found the following affinity series: Cu(II) > Co(II) > Ni(II) > Zn(II) Fe(III). These anion exchangers can be applied in the removal of copper(II) complexes from waters and wastewaters.  相似文献   

11.
In this study, the water-soluble polymers of N-maleoyl glycine (MG) with crotonic acid (CA) were copolymerized by free radical polymerization to obtain hydrophilic polymers, in order to study the effect of the functional groups in the copolymers on the metal ion retention capacity, electrochemical and thermal behavior, since that important requirements for their use in technological applications are: high solubility in water, chemical stability, a high affinity for one or more metal ions, and selectivity for the metal ion of interest. The metal complexation properties of poly(MG-co-CA) for the metal ions were investigated at pH 3, 5, and 7 in aqueous solution. The metal ion investigated were: Cu(II), Co(II), Cr(III), Ni(II), Cd(II), Zn(II), and Fe(III). The polymeric systems showed high metal ion retention for Zn (II) and Fe(III) at different pH. At different pHs, the MRC of the poly(MG-co-CA) for Fe(III) ions varied from 122.1 to 146.2 mg/g and from 120.5 to 133.5 mg/g, (samples 1 and 2 at pH 3 and 7, respectively). The MRC had the highest retention values for both copolymer systems at pH 7. The copolymers presented higher thermal decomposition temperature (TDT) in comparison with copolymer–metal complexes at pH 3 and 5. The cyclic voltammetry (CV) for poly(MG-co-CA) (20 mM) was compared with the CV of the [poly(MG-co-CA)–Fe(III)] copolymer complex. Moreover, [poly(MG-co-CA)–Fe(III)] showed a redox wave difference between +0.25 and +0.50 V possibly due to the presence of metal complexed with the polymer. The electrochemical characterization of the copolymer poly(MG-co-AC) shown the reduction of carboxylic acid groups of the N-maleoylglycine and crotonic acid moiety to hydroxyl group. The results support the assumption that the copolymer presents convenient electroactivity.  相似文献   

12.
A chromotropic ferrocenyl chalcone with two pyrenyl groups (Fc-dPyr) is prepared and spectroscopically characterized. The X-ray structure analysis shows that the two pyrenyl groups are almost parallel to each other with a torsion angle of 5.57° and adopt a dimeric mode with a distance of 3.776 Å between them, ready to form an excimer. The solvatochromic fluorescence spectra indicate that the emission maxima observed in hydrogen-bonding donor (HBD) solvents (CHCl3, EtOH and MeOH) exhibit a strictly linear relationship with the normalized ETN value, while those in a non-HBD solvent (CH3CN) do not. The molecular chemosensor activity of Fc-dPyr is highly selective toward Fe(III) ions over Fe(II) ions. The fluorescence emission intensity of Fc-dPyr steeply decreases in the presence of Fe(III) ions as an oxidant, but not in the presence of Fe(II) ions.  相似文献   

13.
Radical copolymerization of 1-vinyl-2-pyrrolidone with itaconic acid at different feed monomer ratios (75–25 mol %) were investigated. The copolymers were characterized by elemental analysis, Fourier transform infrared (FTIR), 1H and 13C NMR spectroscopy. The copolymer composition was determined from elemental analysis and found to be statistical copolymers. Additionally, viscosimetric measurements, molecular weight, and polydispersity have been determined. The metal complexation of poly(1-vinyl-2-pyrrolidone-co-itaconic acid) for the metal ions such as Cr(III), Co (II), Zn(II), Ni(II), Cu(II), Cd(II), and Fe(III) were investigated at pH 3, 5, and 7 in aqueous solution. The metal ion interaction with hydrophilic polymers was determined as a function of the pH and filtration factor. Poly(1-vinyl-2-pyrrolidone-co-itaconic acid) showed a high affinity for the metal ions at pH 5 and 7. The poly(NVP-co-IA), with a copolymer composition of 29 : 71 mol % (PVA-3), presented the highest metal ion retention values, particularly at higher pHs, at which the carboxylic acid groups are nonprotonated and could easily coordinate with the metal ions. According to the interaction pattern obtained, Cr(II), Zn(II), Pb(II), and Ni(II) formed the most stable complexes at pH 7. The thermal behaviors of the copolymer and polymer metal complex were characterized using differential scanning calorimetry (DSC) and thermogravimetry techniques under nitrogen atmosphere. The copolymers present high thermal stability and do not present glass transition in DSC curves between 25 and 500°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008  相似文献   

14.
Co(II), Cu(II), Zn(II) and Fe(III) complexes of diisopropylthiourea have been synthesized and characterized by elemental analyses, molar conductivity, magnetic susceptibility, FTIR and electronic spectroscopy. The compounds are non-electrolytes in solution and spectroscopic data of the complexes are consistent with 4-coordinate geometry for the metal(II) complexes and six coordinate octahedral for Fe(III) complex. The complexes were screened for their antibacterial activities against six bacteria: Escherichia coli, Pseudomonas auriginosa, Klebsiella pneumoniae, Bacillus cereus, Staphylococcus aureus and Bacillus pumilus. The complexes showed varied antibacterial activities and their minimum inhibitory concentrations (MICs) were determined.  相似文献   

15.
Catalase‐like activity of the metal complexes of various crosslinked polystyrene‐supported Schiff bases were carried out and correlated with the nature and degree of crosslinking in the polymer support. Polystyrenes with 2–20 mol % ethyleneglycol dimethacrylate (EGDMA), 1,4‐butanediol dimethacrylate (BDDMA) and 1,6‐hexanediol diacrylate (HDODA) were used as polymer supports. functions of diethylenetriamine and salicylaldehyde were incorporated to the chloromethylpolystyrene by polymer analogous reactions and complexed with Fe(II), Fe(III), Co(II), Ni(II), and Cu(II) ions. The metal uptake decreased in the order: Cu(II) > Co(II) > Ni(II) > Fe(III) > Fe(II), and extent of metal uptake by the various crosslinked system varied with the nature and degree of the crosslinking agent. The polymeric ligands and the metal complexes were characterized by various analytical techniques. The catalytic activities of these metal complexes were investigated towards the decomposition reaction of hydrogen peroxide. Generally among the various metal complexes, the catalytic activities decreased in the order: Co(II) > Cu(II) > Ni(II) > Fe(III) ? Fe(II). With increasing rigidity of the crosslinking agent their catalytic activity also decreased. Of the various crosslinked systems, the catalytic activity decreased in the order: HDODA‐ > BDDMA‐ > EGDMA‐crosslinked system. Also, the catalytic activity is higher for low crosslinked systems and decreased further with increasing degree of crosslinking. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1271–1278, 2004  相似文献   

16.
Copolymer of poly(styrene-co-n-caprylamide maleic acid) (PSCMA, defined as HL) and its lanthanide complexes Ln(L)3·6H2O (Ln = Eu and Tb) had been synthesized and characterized by elemental analysis, X-ray diffraction, Fourier transform infrared spectra, UV-spectrophotometer and thermal analysis (TG–DTA). The fluorescence properties of the HL ligand and the Ln(L)3·6H2O complexes in the solid state were investigated. At room temperature, the HL ligand had a strong broad emission band at 410–575 nm (λmax = 458 nm) under excitation at 380 nm, while the respective characteristic emission of Eu(III) and Tb(III) ions was observed in Ln(L)3·6H2O complexes. This demonstrated that the HL ligand in the extra-framework channels succeeded in sensitizing Eu(III) and Tb(III) ions emission. Compared with the Eu(L)3·6H2O complex, the fluorescence intensity of the Tb(L)3·6H2O complex was much stronger. This indicated that the lowest excited triplet state energy level of HL matched well with the excited state energy level of Tb(III). With the increase of the Ln(III) ions content below 15 wt%, the fluorescence intensity increased monotonically. All the Ln(L)3·6H2O complexes exhibited high quantum yield, long fluorescence lifetime and good thermal stability.  相似文献   

17.
A series of iron-polyethylenediaminecarbosilazane (PEDCSZ-Fe) macromolecular chloride macromolecular complexes were prepared by the reaction of Fe(II), Fe(III), and mixed valence Fe(II-III) chlorides with polyethylenediaminecarbosilazane matrix in toluene under inert atmosphere. The mixed valence macromolecular complexes composed of three different ratios of Fe(II)/Fe(III) (1:2, 1:1, and 2:1). Mössbauer spectra were recorded for the samples at room temperature. The spectra of the PEDCSZ-Fe(II) and PEDCSZ-Fe(III) macromolecular complexes showed pure paramagnetic phase, whereas, the spectra for the mixed valence PEDCSZ-Fe(II-III) showed both magnetic and paramagnetic splitting. The magnetic splitting is so broad such that it was fitted with three magnetic sextets and one quadrupole doublet. The relative intensity of the magnetic phase was the highest for the PEDCSZ-Fe(II-III) with 1:1 ratio. The magnetic phase could be attributed to an iron oxide phase (Fe3O4 or FeOOH phase) in a fine powder form as it is clear from the Mössbauer parameters. The XRD patterns of the PEDCSZ-Fe(II-III) with 1:1 ratio contained additional diffraction peaks similar to those observed for Fe3O4 in a fine particle form.  相似文献   

18.
Oligomeric polyester, namely poly(tetramethylene asparate) (PTMA), was synthesized From D ,L ‐aspartic acid and 1,4‐butanediol by a melt codensation technique. Polyester–metal complexes were synthesized by the reaction of PTMA with hydrated acetates of Fe(III), Pd(IV), and UO2(II) in DMSO. The polyester–metal complexes were characterized by elemental analysis, UV–Vis, IR spectral studies, magnetic susceptibility measurements and 1H‐NMR. Mossbauer spectra of mixed samples of Pd‐PTMA and Fe(II)‐PTMA with a ratio of 1 : 2 mol showed the iron(III) oxide formed in early stages of the decomposition at 250°C is mainly fine‐grained and as the temperature is increased, well‐crystalline hematic is formed. Above 250°C, the Mossbauer spectrum showed the typical six‐line pattern of magnetically oriented Fe(III) oxide, but at 800°C, the spectrum showed quadrupole interaction characteristic of PdFe2O4 spinel. The metal ions were found to be six—coordinated with two water molecules as additional ligands besides oxygen and nitrogen atoms of polyester repeating units. Thermogravimetric analysis (DTA‐TG) showed that co‐ordination polymers are thermally more stable than polyester; the activation parameters for both decomposition steps were calculated and discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 942–947, 2004  相似文献   

19.
Interest in developing selective and sensitive metal sensors for environmental, biological, and industrial applications is mounting. The goal of this work was to develop a sensitive and selective sensor for certain metal ions in solution. The goal was achieved via (i) preparing the sensor ((E)-2-((pyridine-3-ylimino)methyl)phenol) (3APS) using microwave radiation in a short time and high yield and (ii) performing spectrophotometric titrations for 3APS with several metal ions. 3APS, a Schiff base, was prepared in 5 min and in a high yield (95%) using microwave-assisted synthesis. The compound was characterized by FTIR, XRD, NMR, and elemental analysis. Spectrophotometric titration of 3APS was performed with Al(III), Ba(II), Cd(II), Co(II), Cu(II), Fe(III), Mn(II), Ni(II), and Zn(II). 3APS showed good abilities to detect Al(III) and Fe(III) ions fluorescently and Cu(II) ion colorimetrically. The L/M stoichiometric ratio was 2:1 for Cu(II) and 1:1 for Al(III) and Fe(III). Low detection limits (μg/L) of 324, 20, and 45 were achieved for Cu(II), Al(III), and Fe(III), respectively. The detection of aluminum was also demonstrated in antiperspirant deodorants, test strips, and applications in secret writing. 3APS showed high fluorescent selectivity for Al(III) and Fe(III) and colorimetric selectivity towards Cu(II) with detection limits lower than corresponding safe drinking water guidelines.  相似文献   

20.
By the reaction of the tetradentate Schiff base ligand H2salbn, N,N-disalicylidene-1,4-diaminobutane with FeIIICl3·6H2O in the presence of Et3N in MeOH a dinuclear iron(III) complex, [FeIII(salbn)(μ-OMe)]2 (1), has been obtained, whereas in EtOH, dinuclear complexes, [FeIII(μ-salbn)]2(μ-O) (2) and [FeIII(salbn)]2(μ-salbn) (3), are obtained. The structure of the complex 1 consists of two Fe(III) centers with one tetradentate salbn ligand (N2O2) which are bridged by two methoxo groups to yield a planar Fe2O2 core. On the other hand, in the complex 2, each of the two Fe(III) ions has a five-coordinate structure in which both salbn ligands act as a bridging didentate ligand and one oxygen atom bridges two Fe(III) ions to form a μ-oxo structure. The structure of the complex 3, which was obtained by accompanying with complex 2, consists of two six-coordinate Fe(III) centers in which each Fe(III) ion is coordinated by a tetradentate salbn ligand (N2O2) and one bridging salbn ligand (NO).  相似文献   

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