首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 36 毫秒
1.
A new dinuclear RuII polypyridyl complex, [(bpy)2Ru(H2bpip)Ru(bpy)2]4+ ( RuH2bpip , bpy=2,2‐bipyridine, H2bpip=2,6‐pyridyl(imidazo[4,5‐f][1,10]phenanthroline), was developed to act as a one‐ and two‐photon luminescent probe for biological Cu2+ detection. This RuII complex shows a significant two‐photon absorption cross section (400 GM) and displays a remarkable one‐ and two‐photon luminescence switch in the presence of Cu2+ ions. Importantly, RuH2bpip can selectively recognise Cu2+ in aqueous media in the presence of other abundant cellular cations (such as Na+, K+, Mg2+, and Ca2+), trace metal ions in organisms (such as Zn2+, Ag+, Fe3+, Fe2+, Ni2+, Mn2+, and Co2+), prevalent toxic metal ions in the environment (such as Cd2+, Hg2+, and Cr3+), and amino acids, with high sensitivity (detection limit≤3.33×10?8 M ) and a rapid response time (≤15 s). The biological applications of RuH2bpip were also evaluated and it was found to exhibit low cytotoxicity, good water solubility, and membrane permeability; RuH2bpip was, therefore, employed as a sensing probe for the detection of Cu2+ in living cells and zebrafish.  相似文献   

2.
A new Cu(II)‐imprinted salen functionalized silica gel adsorbent was synthesized by surface imprinting technique and was employed as a selective solid phase extraction material for Cu2+ removal from aqueous solutions. The samples were characterized by FT‐IR, 1HNMR, 13CNMR, CHNS and DTG techniques. The BET surface area of the silica gel was also determined. The adsorbent was then used for removal of Cu2+ from aqueous solutions under different experimental conditions. It was concluded that the synthesized imprinted silica gel had higher selectivity and capacity compared to the non‐imprinted silica gel and the maximal adsorption capacity of 67.3 and 56.5 mg.g?1 was obtained respectively for ion‐imprinted and non‐imprinted adsorbents. The relative selectivity factor (β) of 50.32 and 31.94 was obtained respectively for Cu2+/Ni2+ and Cu2+/Zn2+ pairs. The dynamic adsorption capacity of the imprinted adsorbent was close to the static adsorption capacity due to the fast kinetic of adsorption. Furthermore, the ion‐imprinted adsorbent was recovered and repeatedly used and satisfactory adsorption capacity with acceptable precision was obtained. Each experiment was repeated at least for three times and the mean and the standard deviation for each measurement were calculated. The applicability of the method was examined for Zayandehrood water as real sample. Acceptabe standard deviation was obtained.  相似文献   

3.
The competitive removal of Pb2+, Cu2+, and Cd2+ ions from aqueous solutions by the copolymer of 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid (AMPS) and itaconic acid (IA), P(AMPS‐co‐IA), was investigated. Homopolymer of AMPS (PAMPS) was also used to remove these ions from their aqueous solution. In the preparation of AMPS–IA copolymer, the molar percentages of AMPS and IA were 80 and 20, respectively. In order to observe the changes in the structures of polymers due to metal adsorption, FTIR spectra by attenuated total reflectancetechnique and scanning electron microscopy (SEM) pictures of the polymers were taken both before and after adsorption experiments. Total metal ion removal capacities of PAMPS and P(AMPS‐co‐IA) were 1.685 and 1.722 mmol Me2+/gpolymer, respectively. Experimental data were evaluated to determine the kinetic characteristics of the adsorption process. Competitive adsorption of Pb2+, Cu2+, and Cd2+ ions onto both PAMPS and P(AMPS‐co‐IA) was found to fit pseudo‐second‐order type kinetics. In addition, the removal orders in the competitive adsorption of these metal ions onto PAMPS and P(AMPS‐co‐IA) were found to be Cd2+ > Pb2+ > Cu2+ and Pb2+ > Cd2+ > Cu2+, respectively. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

4.
A new chemosensor for Cu2+ was synthesized based on 1,2,3,4,5,6,7,8,9,10‐decahydroacridine‐1,8‐dione dyes, which exhibited an obvious fluorescent selectivity to the sensing of Cu2+ ions over other cations, such as Na+, K+, Ca2+, Cd2+, Co2+, Hg2+, Mg2+, Mn2+, Ni2+, Zn2+, Ag+ and Pb2+. Moreover, it presented a fluorescent switch function when EDTA was added to the compound‐Cu2+ complex in examined systems.  相似文献   

5.
A chemo‐sensor [Ru(bpy)2(bpy‐DPF)](PF6)2 ( 1 ) (bpy=2,2′‐bipyridine, bpy‐DPF=2,2′‐bipyridyl‐4,4′‐bis(N,N‐di(2‐picolyl))formylamide) for Cu2+ using di(2‐picolyl)amine (DPA) as the recognition group and a ruthenium(II) complex as the reporting group was synthesized and characterized successfully. It demonstrates a high selectivity and efficient signaling behavior only for Cu2+ with obvious red‐shifted MLCT (metal‐to‐ligand charge transfer transitions) absorptions and dramatic fluorescence quenching compared with Zn2+ and other metal ions.  相似文献   

6.
The metal ions in a neutral Zn–MOF constructed from tritopic triacid H3L with inherent concave features, rigid core, and peripheral flexibility are found to exist in two distinct SBUs, that is, 0D and 1D. This has allowed site‐selective postsynthetic metal exchange (PSME) to be investigated and reactivities of the metal ions in two different environments in coordination polymers to be contrasted for the first time. Site‐selective transmetalation of Zn ions in the discrete environment is shown to occur in a single crystal‐to‐single crystal (SCSC) fashion, with metal ions such as Fe3+, Ru3+, Cu2+, Co2+, etc., whereas those that are part of 1D SBU sustain structural integrity, leading to novel bimetallic MOFs, which are inaccessible by conventional approaches. To the best of our knowledge, site‐selective postsynthetic exchange of an intraframework metal ion in a MOF that contains metal ions in discrete as well as polymeric SBUs is heretofore unprecedented.  相似文献   

7.
Transition metal complexes of arginine (using Co(II), Ni(II), Cu(II) and Zn(II) cations separately) were synthesized and characterized by FTIR, TG/DTA‐DrTG, UV‐Vis spectroscopy and elemental analysis methods. Cu(II)‐Arg complex crystals was found suitable for x‐ray diffraction studies. It was contained, one mole CuII and Na+ ions, two arginate ligands, one coordinated aqua ligand and one solvent NO3? group in the asymmetric unit. The principle coordination sites of metal atom have been occupied by two N atoms of arginate ligands, two carboxylate O atoms, while the apical site was occupied by one O atom for CuII cation and two O atoms for CoII, NiII, ZnII atoms of aqua ligands. Although CuII ion adopts a square pyramidal geometry of the structure. CoII, NiII, ZnII cations have octahedral due to coordination number of these metals. Neighbouring chains were linked together to form a three‐dimensional network via hydrogen‐bonding between coordinated water molecule, amino atoms and O atoms of the bridging carboxylate groups. CuII complex was crystallized in the monoclinic space group P21, a = 8.4407(5) Å, b = 12.0976(5) Å, c = 10.2448(6) Å, V = 1041.03(10) Å3, Z = 2. Structures of the other metal complexes were similar to CuII complex, because of their spectroscopic studies have in agreement with each other. Copper complex has shown DNA like helix chain structure. Lastly, anti‐bacterial, anti‐microbial and anti‐fungal biological activities of complexes were investigated.  相似文献   

8.
Studies of double‐stranded‐DNA binding have been performed with three isomeric bis(2‐(n‐pyridyl)‐1H‐benzimidazole)s (n=2, 3, 4). Like the well‐known Hoechst 33258, which is a bisbenzimidazole compound, these three isomers bind to the minor groove of duplex DNA. DNA binding by the three isomers was investigated in the presence of the divalent metal ions Mg2+, Co2+, Ni2+, Cu2+, and Zn2+. Ligand–DNA interactions were probed with fluorescence and circular dichroism spectroscopy. These studies revealed that the binding of the 2‐pyridyl derivative to DNA is dramatically reduced in the presence of Co2+, Ni2+, and Cu2+ ions and is abolished completely at a ligand/metal‐cation ratio of 1:1. Control experiments done with the isomeric 3‐ and 4‐pyridyl derivatives showed that their binding to DNA is unaffected by the aforementioned transition‐metal ions. The ability of 2‐(2‐pyridyl)benzimidazole to chelate metal ions and the conformational changes of the ligand associated with ion chelation probably led to such unusual binding results for the ortho isomer. The addition of ethylenediaminetetraacetic acid (EDTA) reversed the effects completely.  相似文献   

9.
Understanding the polymorphic states of metal amyloid β (Aβ) interactions helps to elucidate metal‐mediated events in the pathogenesis of Alzheimer's disease. Systematic investigations on the effects of metal ions such as Cu2+ and Zn2+ on the structural and thermodynamic properties of Aβ at the molecular lever seem desirable. In this study, a set of new AMBER force field parameters was developed to model various Cu2+ coordination spheres of Aβ. These parameters including force constants and partial charges obtained using restrained electrostatic potential method were then validated in replica‐exchange molecular dynamics simulations on six Cu2+‐Aβ(1–16) systems. The Cu2+ coordination geometry differs depending on the Cu2+ binding fashions. The structural analyses reveal that Aβ(1–16) prefers turn conformations, which provides a geometrical favor to establish multiple Cu2+ coordination modes in solution at physiological pH. The relative stability of different Cu2+‐Aβ(1–16) complexes was estimated by free energy calculations. The Cu2+ ligands in the most stable Cu2+‐Aβ(1–16) structure involve Glu3, His6, His13 and His14 in terms of MM/3D‐RISM (molecular mechanics/three‐dimensional reference interaction site model). The solvation free energy and conformational entropy calculated by 3D‐RISM method suggest that the binding of Cu2+ within Aβ(1–16) is a spontaneous process. The overlap of the preparation free energy distributions demonstrates the heterogeneous states of Aβ(1–16) conformations that are ready for Cu2+ binding whereas the populations of such polymorphic states may shift at differing pH. © 2013 Wiley Periodicals, Inc.  相似文献   

10.
Decarboxylative cross‐coupling reactions of substituted 2‐carboxyazine N‐oxides, with a variety of (hetero)aryl halides, by bimetallic Pd0/CuI and Pd0/AgI catalysis are reported. Two possible pathways, a conventional bimetallic‐catalyzed decarboxylative arylation, as well as a protodecarboxylative/direct C?H arylation sequence have been considered. These methods provide the first general decarboxylative arylation methodology for the 2‐carboxyazine series.  相似文献   

11.
In the centrosymmetric dinuclear anions of the title bimetallic complex, {[Mg(H2O)6][Cu2(C8H2NO7)2]·2H2O}n, each CuII ion is strongly coordinated by four O atoms in a distorted square‐planar geometry. Two of these O atoms belong to phenolate groups and the other two to carboxylate groups from 5‐nitro‐2‐oxidoisophthalate (L1) trianions, derived from 5‐nitrobenzene‐1,2,3‐tricarboxylic acid (O2N–H3L). The phenolate O atoms bridge the two CuII ions in the anion. In addition, each CuII cation interacts weakly with a symmetry‐related carboxylate O atom of an adjacent L1 ligand, giving a square‐pyramidal coordination geometry. The copper residue forms a ladder‐like linear coordination polymer via L1 ligands. The [Mg(H2O)6]2+ cations sit on centres of inversion. The polymeric anions, cations and free water molecules are self‐assembled into a three‐dimensional supramolecular network via O—H...O hydrogen bonds.  相似文献   

12.
A functionalized cyclam was synthesized by the attachment of a polymerizable acryloyl group to one of the four nitrogens on the cyclam molecule. The polymerization of the functionalized cyclam was performed with N‐isopropylacrylamide and N,N′‐methylene bisacrylamide, and the gels obtained were studied in the presence of different transition‐metal‐ion solutions. There was a drastic difference in the phase‐transition temperature (Tc) of the poly(N‐isopropylacrylamide) (PNIPAAm)/cyclam gel in comparison with the pure PNIPAAm gel. For the described system, a Tc shift of 15 °C was obtained. The presence of functionalized cyclam increased the hydrophilicity and Tc of the aforementioned polymer gels in deionized water (at pH 6) because of the presence of protonated amino moieties. The PNIPAAm/cyclam gels showed a dependence of the swelling behavior on pH. Tc of the pure PNIPAAm gel was weakly influenced by the presence of any transition‐metal ions, such as Cu2+, Ni2+, Zn2+, and Mn2+. The addition of Cu2+ or Ni2+ to the PNIPAAm/cyclam gel reduced Tc of the polymer gel, and a shift of approximately 12 °C was observed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1594–1602, 2003  相似文献   

13.
A dual‐function fluorescence resonance energy transfer (FRET)‐based fluorescent and colorimetric probe was rationally fabricated from an energy donor coumarin moiety and an energy acceptor rhodamine moiety linked by a thiohydrazide arm for selective detection of Hg2+ and Cu2+. Two distinct mechanisms were used for the selective detection. Results revealed that probe 1 showed high fluorescent selectivity towards Hg2+ and evident colorimetric selectivity for Cu2+, which was suitable for ‘naked‐eye’ detection.  相似文献   

14.
A general molecular mechanics (MM) model for treating aqueous Cu2+ and Zn2+ ions was developed based on valence bond (VB) theory and incorporated into the atomic multipole optimized energetics for biomolecular applications (AMOEBA) polarizable force field. Parameters were obtained by fitting MM energies to that computed by ab initio methods for gas‐phase tetra‐ and hexa‐aqua metal complexes. Molecular dynamics (MD) simulations using the proposed AMOEBA‐VB model were performed for each transition metal ion in aqueous solution, and solvent coordination was evaluated. Results show that the AMOEBA‐VB model generates the correct square‐planar geometry for gas‐phase tetra‐aqua Cu2+ complex and improves the accuracy of MM model energetics for a number of ligation geometries when compared to quantum mechanical (QM) computations. On the other hand, both AMOEBA and AMOEBA‐VB generate results for Zn2+–water complexes in good agreement with QM calculations. Analyses of the MD trajectories revealed a six‐coordination first solvation shell for both Cu2+ and Zn2+ ions in aqueous solution, with ligation geometries falling in the range reported by previous studies. © 2012 Wiley Periodicals, Inc.  相似文献   

15.
《Electroanalysis》2005,17(4):327-333
Conducting polymers (CP) remain a promising material to construct stable potential all‐solid‐state ion‐selective potentiometric electrodes. The unique properties of poly(3,4‐ethylenedioxythiophene) doped with poly(4‐styrenesulfonate) ions, PEDOT‐PSS: high CP stability and affinity of doping anions towards Cu2+ ions, make it highly attractive for construction of all‐solid‐state copper(II)‐selective electrodes with outstanding selectivity. The additional benefits can arise from solution processability of commercially available PEDOT‐PSS system. This material was highly promising for a new sensor arrangement, i.e. to obtain disposable, planar and flexible all‐plastic Cu2+‐selective electrodes. These sensors can be obtained by casting a commercially available dispersion of PEDOT‐PSS (Baytron P) on a plastic, non‐conducting support material. The CP being both electrical lead and ion‐to‐electron transducer, was covered with plastic, solvent polymeric Cu2+ selective membrane. This extremely simple arrangement, after conditioning in dilute Cu2+ solution, was characterized with linear Nernstian responses within the activities range from: 0.1 to 10?4 M, followed by super‐Nernstian responses for lower activities. The latter result points to effective elimination of primary ions leakage from the plastic membrane / transducer phase and has resulted in significantly improved selectivities. Obtained log K values were equal to ?7.6 for Co2+, ?7.4 for Zn2+, ?7.2 for Ca2+ and ?6.8 for Na+, respectively.  相似文献   

16.
The intrinsic binding ability of 7 natural peptides (oxytocin, arg8‐vasopressin, bradykinin, angiotensin‐I, substance‐P, somatostatin, and neurotensin) with copper in 2 different oxidation states (CuI/II) derived from different Cu+/2+ precursor sources have been investigated for their charge‐dependent binding characteristics. The peptide‐CuI/II complexes, [M − (n‐1)H + nCuI] and [M − (2n‐1)H + nCuII], are prepared/generated by the reaction of peptides with CuI solution/Cu‐target and CuSO4 solution and are analyzed by using matrix‐assisted laser desorption/ionization (MALDI) time‐of‐flight mass spectrometry. The MALDI mass spectra of both [M − (n‐1)H + nCuI] and [M − (2n‐1)H + nCuII] complexes show no mass shift due to the loss of ─H atoms in the main chain ─NH of these peptides by Cu+ and Cu2+ deprotonation. The measured m/z value indicates the reduction of CuI/II oxidation state into Cu0 during MALDI processes. The number and relative abundance of Cu+ bound to the peptides are greater compared with the Cu2+ bound peptides. Oxytocin, arg8‐vasopressin, bradykinin, substance‐P, and somatostatin show the binding of 5Cu+, and angiotensin‐I and neurotensin show the binding of 7Cu+ from both CuI and Cu targets, while bradykinin shows the binding of 2Cu2+, oxytocin, arg8‐vasopressin, angiotensin‐I, and substance‐P; somatostatin shows the binding of 3Cu2+; and neurotensin shows 4Cu2+ binding. The binding of more Cu+ with these small peptides signifies that the bonding characteristics of both Cu+ and Cu2+ are different. The amino acid residues responsible for the binding of both Cu+ and Cu2+ in these peptides have been identified based on the density functional theory computed binding energy values of Cu+ and the fragment transformation method predicted binding preference of Cu2+ for individual amino acids.  相似文献   

17.
Hui Xu  Xiwen Zeng  Huiling Dai 《中国化学》2011,29(10):2165-2168
A new fluorescent chemosensor based upon 1,8‐naphthalimide and 8‐hydroxyquinoline was synthesized, and its fluorescent properties in the presence of different metal cations (Hg2+, Ag+, Zn2+, Fe2+, Cd2+, Pb2+, Ca2+, Cu2+, Mg2+, and Ba2+) were investigated. It displayed fluorescence quenching with some heavy and transition metal (HTM) ions, and the quenching strongly depended on the nature of HTM ions.  相似文献   

18.
Metal Complexes of Biologically Important Ligands. CLXVI Metal Complexes with Ferrocenylmethylcysteinate and 1,1′‐Ferrocenylbis‐(methylcysteinate) as Ligands A series of complexes of transition metal ions ( Cr3+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+ ) and of lanthanide ions ( La3+, Nd3+, Gd3+, Dy3+, Lu3+ ) with the anions of ferrocenylmethyl‐L‐cysteine [(C5H5)Fe(C5H4CH(R)SCH2CH(NH3+)CO2?] (L1) and with the dianions of 1,1′‐ferrocenylbis(methyl‐L‐cysteine) [Fe(C5H4CH(R)SCH2CH(NH3+) CO2?)2] (R = H, Me, Ph) (L2) as N,O,S‐donors were prepared. With the monocysteine ferrocene derivative L1 as ligands complexes [MIIL12] or [CrIIIL12]Cl type complexes are formed whereas the bis(cysteine) ligand L2 yields insoluble complexes of type [ML2]n, presumably as coordination polymers. The magnetic moments of [MnIIL2]n, [PrIIIL2]n(OH)n and [DyIIIL2]n(OH)n exhibit “normal” paramagnetism.  相似文献   

19.
An amphoteric polyamidoamine (PAA)‐based hydrogel, named INT‐PAA1, with a novel molecular architecture was prepared and studied as a Co2+‐, Ni2+‐, and Cu2+‐sorbing material. This hydrogel was obtained by the synthesis of a PAA in the presence of a second presynthesized PAA carrying many primary amino groups as side substituents, which acted as a macromolecular crosslinking agent. Therefore, it had an intersegmented structure. INT‐PAA1 exhibited a remarkable sorption capacity and sorption rate for Co2+, Ni2+, and Cu2+ that were advantageously in situ monitored by cyclic voltammetry. An extended X‐ray absorption fine structure spectroscopy characterization of the Co2+/INT‐PAA1 complex was also performed. The very fast and quantitative metal‐ion uptake, made apparent by an intense coloring of the hydrogel, showed remarkable potential for environmental applications such as heavy‐metal detection, recovery, and elimination. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2316–2327, 2006  相似文献   

20.
Waste poly(p‐phenylene terephthalamide) fibers (PPTA) were chemically modified through nitration and nitro‐reduction reactions to obtain nitro‐ and amino‐containing fibers and used as adsorbents for metal ions. The structures of the modified fibers were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X‐ray diffraction (XRD), and thermogravimetric (TG) analysis. Metal ions, such as Ni2+, Pb2+, Cu2+, and Hg2+, were used to determine the adsorption capacities of the PPTA fibers before and after modification in aqueous solutions. The results showed that the modification improved the adsorption capability of fibers and extraction ratio of metal ions significantly. The adsorption mechanism of modified PPTA fibers for metal ions was proposed. The adsorption processes of Ni2+, Pb2+, and Cu2+ followed well a pseudosecond‐order model onto PPTA‐NH2. The Langmuir and Freundlich models were employed to fit the isothermal adsorption. The results revealed that the linear Langmuir isotherm model is better‐fit model to predict the experimental data. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号