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1.
Brajter K  Słonawska K 《Talanta》1980,27(9):745-750
The possibility of using NTA, EDTA and DTPA as complexing agents for separation of some platinum group ions on cellulose ion-exchangers has been investigated. The greatest differences in the affinities of Pd(II) and Pt(IV) toward the cellulose ion-exchangers are obtained in the presence of DPTA, Cellex D (as ion-exchanger) in hydroxide form. The column separation of Pd(II) from Pt(IV), Rh(III) from Pd(II) and of a Rh(III)Pd(II)Pt(IV) mixture can be achieved with DPTA and chloride solutions. The method can be for determination of the components of RhPdPt alloys.  相似文献   

2.
Dalvi AA  Satpati AK  Palrecha MM 《Talanta》2008,75(5):1382-1387
Characteristics of the adsorption/electro-reduction of Pt/Rh hexamethylene tetramine (HMTA) complex on static mercury drop electrode surface were studied. Cyclic voltammetry was carried out to get the insight about the mechanistic behaviour of the catalytic current obtained in the voltammetric scan of Pt/Rh HMTA complex in acidic solution. Adsorptive stripping voltammetry using HMTA as the complexing agent was found to be highly sensitive method for the determination of Pt/Rh. Voltammetric measurements were carried out using hanging mercury drop electrode (HMDE) as the working electrode, a glassy carbon rod as the counter and an Ag/AgCl/KClsaturated as the reference electrode. Various electrochemical parameters like deposition potential, deposition time, concentration of the ligand, supporting electrolyte etc. were optimized. The detection limit of Pt and Rh was found to be 4.38 pML−1 and 2.80 pML−1, respectively for the deposition time of 30 s. Simultaneous determination of Pt(II) and Rh(III) in water samples was possible. The method was found to be free from the commonly occurring interfering ions such as Cu(II), Cd(II), Zn(II), Pb(II), Cr(III), Cr(VI), Fe(III), Fe(II), Ni(II) and Co(II). Spike recovery tests for both Pt and Rh in tap water and sea water samples were also carried out. The method has been verified by analyzing certified reference material (WMG-1).  相似文献   

3.
Five salts, [(C(4)H(9)N(4))Pt(II)(CNCH(3))(2)](BPh(4)).CH(3)OH, [(C(4)H(9)N(4))Pt(II)(CNCH(3))(2)](PF(6)).CH(2)Cl(2), [(C(4)H(9)N(4))Pt(II)(CNCH(3))(2)]Cl.4H(2)O, [(C(4)H(9)N(4))Pt(II)(CNCH(3))(2)]Br.3.5H(2)O, and [(C(4)H(9)N(4))Pt(II)(CNCH(3))(2)]Cl.0.1H(2)O, have been crystallized and examined by single crystal X-ray diffraction. While the internal structure of the cation is similar in all salts, the interactions between cations vary in the different salts. Yellow [(C(4)H(9)N(4))Pt(II)(CNCH(3))(2)](BPh(4)).CH(3)OH and red [(C(4)H(9)N(4))Pt(II)(CNCH(3))(2)](PF(6)) form face-to-face dimers with Pt...Pt separations of 3.6617(6) and 3.340(2) A, respectively. In the latter, hydrogen bonding of the chelating ligand to adjacent anions facilitates the close approach of pairs of cations. The salts [(C(4)H(9)N(4))Pt(II)(CNCH(3))(2)]Cl.4H(2)O, [(C(4)H(9)N(4))Pt(II)(CNCH(3))(2)]Br.3.5H(2)O, and [(C(4)H(9)N(4))Pt(II)(CNCH(3))(2)]Cl.0.1H(2)O form columnar structures with Pt...Pt separations that range from 3.2514(5) to 3.5643(6) A. The water molecules and anions surround these columns and form bridges between neighboring columns. The electronic spectra of aqueous solutions of [(C(4)H(9)N(4))Pt(II)(CNCH(3))(2)]Cl.4H(2)O show spectral changes upon increasing concentrations of the platinum complex that are indicative of the formation of a dimer in solution with an equilibrium constant for dimerization of 23(1).  相似文献   

4.
The thiocyanate complexes of Pd(II), Pt(II) and Pt(IV) were studied by capillary zone electrophoresis. Pd(II) can be detected in the form of the thiocyanate complex at 305 nm with higher sensitivity than in the form of its chloro complex (absorption maximum 214 nm). A detection limit equal to 5 ppb for Pd has been finally achieved. The possibility of simultaneous determination of Pd(II) and Pt(IV) in the form of thiocyanate complexes has also been demonstrated. When the method optimized for the determination of Pt(II) was applied to the drugs Cykloplatin and Ribocarbo (containing carboplatin) and Platidiam (containing cisplatin), good agreement of the platinum content with the declared value was obtained. Samples of vehicle exhaust particulates (National Institute for Environmental Studies, Japan, No. 8 reference material) were also analyzed.  相似文献   

5.
《Analytical letters》2012,45(8):917-926
Abstract

An analytical method has been developed to measure Pt(II) in urine via derivatization and UV or HPLC analysis. A measured quantity of urine is heated briefly with diethyl ammonium diethyl-dithiocarbamate, and the resulting Pt(Et2NCS2)2 is extracted into a measured volume of chloroform. Concentrations of Pt(II) are determined by UV absorption at 346 nm or by reverse phase HPLC analysis. The detection limit for Pt(II) as its dithiocarbamate is ~ 1 ng by HPLC; the concentration limit for HPLC analysis by direct extraction was ~ 25 ng/ml. Chromatographic response was linearly related to Pt(II) concentration over the range 100-4, 000 ng/ml; dilution of more concentrated samples has extended this range to at least 30, 000 ng/ml. This method has been applied to the analysis of Pt(II) in the urine of patients who have received cis-dichlorodiamniineplatinum(II) (CDDP) chemotherapy.  相似文献   

6.
Abstract

A new water-soluble platinum(II) complex, [Pt(CEX)Cl(DMSO)]Cl (CEX is cephalexin), was synthesized and characterized by physicochemical, spectroscopic, and computational methods. Multispectroscopic techniques were used to investigate the interaction of Pt(II) complex with human serum albumin (HSA) under the physiological conditions. The results of fluorescence titration indicated that the binding of the Pt(II) complex to HSA induced fluorescence quenching through static quenching mechanism with binding constant of 1.24?×?104?M?1 at 298?K. The thermodynamic parameters at different temperatures indicated that van der Waals forces, hydrogen bonds, and electrostatic forces play major roles in the stability of Pt(II) complex–HSA association. The displacement experiments using the site probes warfarin and ibuprofen substantiated that Pt(II) complex could bind to both site I and II of HSA. Furthermore, UV–Vis and fluorescence spectra were used to investigate the conformational changes of HSA molecule with the addition of Pt(II) complex. The binding constant of Pt(II) complex is more than two orders of magnitude higher than the corresponding value of cephalexin. These results indicate that the binding affinity of Pt(II) complex is stronger than the free drug. In addition, the antibacterial study showed that the MIC of platinum complex of cephalexin for variety of organisms was lower than free cephalexin.  相似文献   

7.
Using the Voronoi–Dirichlet partition procedure and the method of intersecting spheres, it is demonstrated that in the crystal structures of chalcogen-containing compounds, Pt(IV) atoms form only PtX6 octahedra (X = S, Se, Te), whereas in the case of Pt(III) and Pt(II), square coordination by X atoms is typical. The Pt(II) atoms can also form PtX5 square pyramids (X = S, Se), PtS6 octahedra, and PtTe3Pt3 quasi-octahedra in which a platinum atom is located in the trans-position to each coordinated tellurium atom. It was found that Pt(II) atoms in the PtX4 squares (X = S, Se), unlike square-coordinated Pt(III) atoms, can form one or two Pt–M bonds (M is a d metal) and 1 to 4 secondary Pt–Q bonds, where Q is an s metal or hydrogen. The main features of platinum stereochemistry depending on the metal valence state and coordination number (CN) and on the nature of the chalcogen atom were quantitatively characterized in terms of the Voronoi–Dirichlet polyhedra.  相似文献   

8.
The reaction of cis-[Pt(NH3)2(3-pyhaH)2]2+ (3-pyhaH = 3-pyridinehydroxamic acid) and cis-[Pt(NH3)2(4-pyhaH)2]2+ (4-pyhaH = 4-pyridinehydroxamic acid) with Cu(II), Ni(II) or Zn(II) in aqueous solution affords novel heterobimetallic pyridinehydroxamate-bridged complexes, {cis-[Pt(NH3)2(mu-3-pyha)M(mu-3-pyha)].SO4.xH2O}n and {cis-[Pt(NH3)2(mu-4-pyha)M(mu-4-pyha)].SO4.xH2O}n respectively. The crystal and molecular structure of one of these, {cis-[Pt(NH3)2(mu-3-pyha)Cu(mu-3-pyha)]SO4.8H2O}n 3a, has been determined and was found to be a novel heterobimetallic wave-like coordination polymer, the structure of which contains interlinked pyridinehydroxamate-bridged repeating units of Pt(II) and Cu(II) ions in slightly distorted square-planar N4 and O4 coordination environments respectively and extensive hydrogen-bonding through the Pt ammines and the deprotonated hydroxamate O and via the O of the SO4(2-) counterions and the H(N) of the hydroxamate moiety. Spectrophotometric and speciation studies on the other heterobimetallic systems confirm that very similar species are being formed in solution and based on elemental analysis and spectroscopic results analogous complexes are formed in the solid-state. In this paper, we report the first examples of coordination polymers incorporating both Pt(II)/Cu(II), Pt(II)/Ni(II) and Pt(II)/Zn(II) and containing pyridinehydroxamic acids as bridging scaffolds.  相似文献   

9.
A robust reversed phase ion-pairing RP-HPLC method has been developed for the unambiguous speciation and quantification of all possible homoleptic and heteroleptic octahedral platinum(IV) [PtCl(6-n)Br(n)](2-) (n=0-6) as well as the corresponding platinum(II) [PtCl(4-n)Br(n)](2-) (n=0-4) complex anions using UV/Vis detection. High resolution (195)Pt NMR in more concentrated solutions of these Pt(II/IV) complexes (≥50 mM) served to validate the chromatographic peak assignments, particularly in the case of the possible stereoisomers of Pt(II/IV) complex anions. By means of IP-RP-HPLC coupled to ICP-MS or ICP-OES it is possible to accurately determine the relative concentrations of all possible Pt(II/IV) species in these solutions, which allows for the accurate determination of the photometric characteristics (λ(max) and ?) of all the species in this series, by recording of the UV/Vis absorption spectra of all eluted species, using photo-diode array, and quantification with ICP-MS or ICP-OES. With this method it is readily possible to separate and estimate the concentrations of the various stereoisomers which are present in these solutions at sub-millimolar concentrations, such as cis- and trans-[PtCl(4)Br(2)](2-), fac- and mer-[PtCl(3)Br(3)](2-) and cis- and trans-[PtCl(2)Br(4)](2-) for Pt(IV), and cis- and trans-[PtCl(2)Br(2)](2-) in the case of Pt(II). All mixed halide Pt(II) and Pt(IV) species can be separated and quantified in a single IP-RP-HPLC experiment, using the newly obtained photometric molar absorptivities, ?, determined herein at given wavelengths.  相似文献   

10.
Koch KR  Auer D 《Talanta》1993,40(12):1975-1980
Microamounts of Pt(II/IV) (0.25–800 μg/ml) and Pd(II) (5–600 μg/ml) in> 0.5 M hydrochloric acid can readily be determined by means of a simple FIA method based on the selective reaction of tin(II)chloride with these metals. The FIA method has a high linear dynamic range, and is relatively free from interferences of many transition metals, with the exception of Au and Rh; small amounts of other PGMs can be tolerated. Determination of Pt on a hydrogenation catalyst by this method compares well with that found by flame atomic absorption spectroscopy. By monitoring at two or more wavelengths, Pt and Pd can be determined in mixtures by this means, to yield a simple, cost-effective FIA method for possible on-line determinations and quality control of, in particular, Pt containing acidic refinery and other process streams.  相似文献   

11.
Hydrosilylation of cyclohexene and allyl chloride in the presence of Pt(0) complexes with tetramethyldivinyldisiloxane (Karstedt catalyst) and hexavinyldisiloxane was studied. It was shown that these catalysts are much more active in the hydrosilylation of cyclohexene with trichloro-, dichloro(methyl)-, and chlorodimethylsilane than the Pt(II)-containing Speier catalyst. In the hydrosilylation of allyl chloride in the presence of Pt(0) complexes, the ratio of the fraction of addition products to the fraction of reduction products increases from 5.7 (Speier catalyst) to 10–16. Quantum-chemical calculations showed that Pt(0) complexes are more active than Pt(II) complexes on the stage of formation of platinum silicon hydride complexes.  相似文献   

12.
《印度化学会志》2023,100(3):100923
In recent years, various Pt(II) metal complexes with N-based intercalating tridentate ligands, such as dpb, Fdpb, and F2dpb, have been developed which exhibit strong anticancer properties because they effectively bind with DNA nucleobase pairs. Past literature has also revealed that the anticancer activity of such square planer Pt(II)-complexes is fully controlled by the presence of halide groups (viz., –F, -Cl and –I) which are directly attached to the Pt(II) ion or tridentate ligands. The proper active sites within Pt(II)-complexes and the role of Pt-X bond may also theoretically be determined by using a molecular electrostatic potential (MEP) map diagram. Moreover, the quantum mechanical TD-DFT (Time-dependent density-functional theory) method is quite useful for predicting the theoretical UV–Vis spectra for such Pt(II)-complexes, during interaction with AT/GC base pairs. The density-functional theory (DFT) is one of the low-cost theoretical methods which is also a useful tool for investigating the various binding modes for anticancer agents with DNA nucleobases. In this current study, we aim to analyze the proper interaction between some dpb-based Pt(II)-complexes as potent anticancer agents with AT/GC base pairs.  相似文献   

13.
2,6-Diphenylpyridine forms, as twofold-deprotonated, terdentate ligand, complexes with Pt(II) and Pd(II), having two adjacent five-membered metallocycles. As mono-deprotonated, bidentate ligand, it forms cis-bis-complexes having a chirality axis. Pt(II) complexes undergo thermal and photochemical oxidative addition reactions, yielding stable Pt(IV) compounds. Pd(II) complexes yield substitued 2,6-diphenylpyridine in photochemical reactions.  相似文献   

14.
An ion-imprinted polymer (IIP) was obtained by copolymerization of methacrylic acid (as a functional monomer) and ethylene glycol dimethacrylate (as a crosslinking agent) in the presence of various chelators for Pt(II) ion and using 2,2??-azo-bis-isobutyronitrile as the initiator. Specifically, acetaldehyde thiosemicarbazone (AcTSn) and benzaldehyde thiosemicarbazone (BnTSn) were used as chelators. The IIPs were applied as sorbents for solid-phase extraction of Pt(II) and Pt(IV) ions from aqueous solutions. The effects of acidity and flow rate of the sample, of elution conditions and of potentially interfering ions were investigated. The imprinting effect of analyte is clearly demonstrated by the fact that only the IIP is capable of quantitative retention of Pt(II) and Pt(IV) ions. The method works best in the pH range from 0.5 to 1 and from 3.5 to 9.5. The ions can be recovered with an acidic solution of thiourea. The Pt-AcTSn polymer displays better sorption properties for the separation of analytes. The selectivity coefficients of the Pt-AcTSn and control polymers for Pt(IV) in the presence Pd(II), Rh(III), Ru(III), Al(III) and Cu(II) were calculated, and the sorbent capacity for Pt(IV) was found to be 4.56???g?g?-1. The method was successfully applied to the determination of Pt(IV) by electrothermal atomic absorption spectrometry in tap water, tunnel dust and anode slime samples.
Figure
The new ion imprinted polymers based on Pt(II)-thiosemicarbazone derivative chelates were prepared and used as solid phase extraction sorbent for selective separation of platinum. The method was successfully applied to the determination of analyte in environmental samples by electrothermal atomic absorption spectrometry  相似文献   

15.
Sun QF  Wong KM  Liu LX  Huang HP  Yu SY  Yam VW  Li YZ  Pan YJ  Yu KC 《Inorganic chemistry》2008,47(6):2142-2154
By employing functional diimine ligands coordinated dipalladium(II,II) or diplatinum(II,II) clips as corners and the coplanar 4,4'-bipyrazolate dianion (L(2-)) ligand as linker, a series of bipyrazolate-bridged metallo-macrocycles, namely, [M8L4](NO3)8 (M = Pd(dmbpy), 1; Pd(bpy), 2; Pt(bpy), 3a; Pd(phen), 4; Pt(phen), 5; Pd(15-crown-5-phen), 6; Pd(18-crown-6-phen), 8; Pd(benzo-24-crown-8-phen), 10a; Pt(15-crown-5-phen), 7a, Pt(18-crown-6-phen), 9a; Pt(benzo-24-crown-8-phen), 11a) and [M6L3](NO3)6 (M = Pt(bpy), 3b; Pt(15-crown-5-phen), 7b; Pt(18-crown-6-phen), 9b; Pd(benzo-24-crown-8-phen), 10b; Pt(benzo-24-crown-8-phen), 11b), have been synthesized through a directed self-assembly approach that involves spontaneous deprotonation of the 1H-bipyrazolyl ligands in aqueous solution. All these compounds have a crown-shaped cavity that can serve as host to solvent molecules and anions. The structures are characterized by elemental analysis, (1)H and (13)C NMR, ESI-MS, and in the cases of 1a (the BF4(-) salt of 1), 2a (the BF4(-) salt of 2), and 3b by single-crystal X-ray diffraction analysis. Photophysical properties for complexes 1 and 2 are discussed.  相似文献   

16.
A general route for synthesis of six structurally similar Pt(II) diimine thiolate/phenolates chromophores possessing bulky phenolate or thiolate ligands is reported. The Pt chromophores were characterized using an array of techniques including 1H, 13C, and 195Pt NMR, absorption, emission, (spectro)electrochemistry, and EPR spectroscopy. Systematic variation of the electronic structure of the Pt(II) chromophores studied was achieved by (i) changing solvent polarity; (ii) substituting oxygen for sulfur in the donor ligand; (iii) alternating donor ligands from bis- to di-coordination; and (iv) changing the electron donating/withdrawing properties of the ligand(s). The lowest excited state in these new chromophores was assigned to a [charge-transfer-to-diimine] transition from the HOMO of mixed Pt/S (or Pt/O) character on the basis of absorption and emission spectroscopy, UV/vis (spectro)electrochemistry, and EPR spectroscopy. One of the chromophores, Pt(dpphen)(3,5-di-tert-butyl-catecholate) represents an example of a Pt(II) diimine phenolate chromophore that possesses a reversible oxidation centered predominantly on the donor ligand. Results from EPR spectroscopy indicate participation of the Pt(II) orbitals in the HOMO. There is a dramatic difference in the photophysical properties of carborane complexes compared to other mixed-ligand Pt(II) compounds, which includes room-temperature emission and photostability. The charge-transfer character of the lowest excited state in this series of chromophores is maintained throughout. Moreover, the absorption and emission energies and the redox properties of the excited state can be significantly tuned.  相似文献   

17.
The first example for electrogeneration of a Pt(IV) porphyrin from its Pt(II) form is presented and the Pt(II/IV) and reverse Pt(IV/II) oxidation-reduction processes are elucidated by electrochemistry and thin-layer UV-visible spectroelectrochemistry. Three products, [(TPP˙(+))Pt(II)](+), [(TPP)Pt(IV)](2+) and [(TPP˙(+))Pt(IV)](3+), produced by electrooxidation of the Pt(II) porphyrin have been characterized by in situ spectroelectrochemistry and ESR measurements after controlled potential bulk electrolysis. The first definitive evidence for the electrochemical conversion of a Pt(iv) porphyrin to its Pt(II) form is also presented. The potential for this electroreduction is highly dependent upon the nature of the anion, ClO(4)(-) or Cl(-). A mechanism for the reversible conversion between Pt(II) and Pt(IV) tetraphenylporphyrins is proposed.  相似文献   

18.
Novel B,N,N-cyclometallated Pt(II) complexes of 2,2'-bipyridin-6-yl carboranes exhibit absorption and emission similar to relative Pt(II) complexes of aromatic C,N,N-ligands: the same transitions but lower intensities. DFT calculations suggest the former emits from the (3)MLCT state while for the latter the mixed (3)ICT-MLCT transitions should be considered.  相似文献   

19.
The treatment of cis-[Pt(II)(L(1a/b)-S,O)2] complexes of N,N-diethyl- (HL(1a)) and N,N-di(n-butyl)-N'-benzoylthiourea (HL(1b)) with I2 or Br2 in chloroform, leads to rapid oxidative addition to yield several geometric isomers of [Pt(IV)(L-S,O)(2)X(2)](X = I, Br); the reactions can be monitored by (195)Pt NMR and UV-visible spectrophotometry. The products cis-[Pt(IV)(L(1a)-S,O)2I2] and cis-[Pt(IV)(L(1a)-S,O)2Br2], which have been isolated and structurally characterized, are the first-reported crystal structures of complexes of Pt(iv) with this class of ligand. Molecules of 6 pack such that the I-Pt-I axes are essentially aligned, with unusually close nearest-neighbour iodide contacts (3.553(1)A). These short II intermolecular interactions lead to infinite chains of weakly connected molecules in crystals of the compound. No such interactions are evident in the corresponding crystals of . Reaction of the Pt(II) complex of N-propyl-N'-benzoylthiourea (H2L(2a))cis-/trans-[Pt(II)(H2L(2a)-S)2Br2] with Br2 also results in oxidative addition, to yield trans-Pt(IV)(H2L(2a)-S)2Br4. By contrast, treatment of cis-/trans-[Pt(II)(H2L(2a)-S)2I2] with I2 does not lead to an oxidative addition product, yielding instead an interesting iodine inclusion compound of Pt(II), trans-[Pt(II)(H2L(2a)-S)2I2.I2. In 8, short intermolecular II distances of 3.453(1)A between I2 and coordinated iodide ions in trans-[Pt(II)(H(2)L(2a)-S)(2)I(2)] molecules, result in infinite chains of weakly linked trans-[Pt(II)(H2L(2a)-S)2I2]...I2 groups in the lattice. However, the empirically estimated bond order of 0.75 for the included I2 molecules does not support the possible existence of discrete tetraiodide ions (I4(2-)) in the lattice of compound 8.  相似文献   

20.
Platinum-based complexes are among the most widely utilized cancer therapeutics. Current Pt(II) drugs face some challenges including toxicity and drug resistance. To solve these issues, great efforts have been devoted to developing nonclassical platinum complexes, such as Pt(IV) prodrugs, that act via mechanisms distinct from those of the approved drugs. Compared with active Pt(II) counterparts, Pt(IV) complexes are relatively inert. Although direct interactions between Pt(IV) complexes and nucleotides have been reported, the reaction is slow due to the kinetic inertness of Pt(IV) complexes. Herein, we design and synthesize a Pt(IV) monotrifluoromethyl complex, in which the chloride ligand that is trans to trifluoromethyl ligand is reactive. The Pt(IV) monotrifluoromethyl complex is very stable in water but displays high reactivity towards various substrates including buffer components and 5’-dGMP. The study of reaction mechanism reveals that this Pt(IV) complex reacts with phosphate via SN2 nucleophilic substitution pathway, which is different from Pt(II) drugs. The Pt(IV) monotrifluoromethyl complex is cytotoxic in human ovarian cancer cells. Our work reports an example of a reactive organometallic Pt(IV) complex that can directly interact with nucleophiles and implies its potential as an anticancer agent.  相似文献   

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