Complexation of N-bis[2-(1,2-dicarboxyethoxy)ethyl]aspartic acid with Cd(II), Hg(II) and Pb(II) ions in aqueous solution

The persistence of widely used chelating agents EDTA and DTPA in nature has been of concern and there is a need for ligands to replace them. In a search for environmentally friendly metal chelating ligands for industrial applications, complex formation equilibria of N-bis[2-(1,2-dicarboxyethoxy)ethyl]aspartic acid (BCA6) with Cd(II), Hg(II) and Pb(II) in aqueous 0.1 M NaNO₃ solution were studied at 25°C by potentiometric titration. Complexation was modeled and the stability constants of the different complexes were determined for each metal ion using the computer program SUPERQUAD. With all metal ions, stable ML^4? complexes dominated the complex formation. The stabilities of Cd(II), Hg(II) and Pb(II) chelates of BCA6 are remarkably lower than those of EDTA and DTPA. Environmental advantages of the use of BCA6 instead of EDTA and DTPA are better biodegradability and lower nitrogen content with a possibility to save chemicals and process steps in pulp bleaching.     

Cu(II), Zn(II), AND Pb(II) STABILITY CONSTANTS OF CYCLAM AMPHIPHILES

Abstract

1-Hexadecyl-1,4,8,11-tetraazacyclotetradecane (hexadecyl cyclam) and 1-(3,7,11,15-tetramethyl) hexadecyl-1,4,8,11-tetraazacyclotetradecane (tetramethylhexadecyl cyclam) have been synthesized and their deprotonation and ligand-metal formation constants, K, determined for Cu(II), Zn(II) and Pb(II). The coupling of a long hydrocarbon chain to a ring nitrogen decreased the general ability of the cyclam ring to complex with metal ions. The greatest effect appeared to be for Cu(II) decreasing from a pK of 27 for cyclam to about 17. The titrations were fitted by HYPERQUAD and the concentrations of the intermediate complexes obtained as a function of pH. Metal-ligand complexes LMH₂ ⁴⁺, LMH₂₊ and LM₂₊ can coexist through a wide pH range. We have also calculated a composite metal-binding constant, K′, to reflect more accurately the overall ability of these ligands to bind a metal at any particular pH. K′, which is 14.6 for (hexadecyl cyclam)-Cu(II), is constructed from the concentrations of all the metal-chelated species at pH = 7. Generally, K′ is much lower than K.     

Spectrophotometric study of Cd(II), Pb(II), Hg(II) and Zn(II) complexes with 5,10,15,20-tetrakis(4-carboxylphenyl)porphyrin

The reaction of 5,10,15,20-tetrakis(4-carboxylphenyl)porphyrin (TCPP) with Cd(II), Pb(II), Hg(II) and Zn(II) was studied spectrophotometrically and kinetics, equilibrium constants as well as photodecomposition of complexes were determined. It was verified that these metal ions with large radius accelerate the incorporation reaction of zinc into TCPP. On the basis of the mechanism and kinetics of this reaction, a sensitive method for the spectrophotometric determination of trace amounts of Zn(II) has been developed. The molar absorptivity of examined Zn-TCPP complex and Sandell's sensitivity at 423 nm were 3.5×10⁵ M⁻¹ cm⁻¹ and 18.3 ng cm⁻². The detection limit for the recommended procedure was 1.4×10⁻⁹ M (0.9 ng ml⁻¹) and precision in range 20-100 ng ml⁻¹ not exceeds 2.7% RSD. The proposed method applied for zinc determination in natural waters and nutritional supplement was compared with AAS results and declared value.     

Synthesis and characterization of novel Cd(II), Zn(II) and Ni(II) complexes with 2-quinolinecarboxaldehyde selenosemicarbazone. Crystal structure of bis(2-quinolinecarboxaldehyde selenosemicarbazonato)nickel(II)

New complexes of Cd(II), Zn(II) and Ni(II) with 2-quinolinecarboxaldehyde selenosemicarbazone (Hqasesc) were synthesized and structurally characterized. The structure of the ligand, Cd(II) and Zn(II) complexes was determined by NMR and IR spectroscopy, elemental microanalysis and molar conductivity measurements. Both complexes occur in solution in two forms, the major tetrahedral and minor octahedral. In the major Cd(II) complex one qasesc⁻ ligand is coordinated as a tridentate, the fourth coordination site being occupied by acetate, while in the major Zn(II) complex two qasesc⁻ ligands are coordinated as bidentates. In both minor complexes two qasesc⁻ ligands are coordinated as tridentates forming the octahedral geometry around the central metal ion. The only paramagnetic complex in the series is Ni(II) complex for which X-ray structure analysis was performed. The complex has the angularly distorted octahedral geometry with two qasesc⁻ ligands coordinated as tridentates, in a similar way as in the minor complexes of Cd(II) and Zn(II).     

Synthesis and Characterization of Ni(II), Cu(II), Zn(II) and Cd(II) Complexes of a New Vic-Dioxime Ligand

In this study, 1,2-dihydroxyimino-3,7-di-aza-9,10-O-α-methyl benzal decane (LH₂) was synthesized starting from 1,2-O-α-methyl benzal-4-aza-7-amino heptane (RNH₂) and antichloroglyoxime. With this ligand, complexes were synthesized using Ni(II) and Cu(II) salts with a metal:ligand ratio of 1:2. However, the reaction of the ligand with salts of Zn(II) and Cd(II) gave products with metal:ligand ratio of 1:1. Structures of the ligand and its complexes are proposed based on elemental analyses, IR, ¹³C- and ¹H-NMR spectra, magnetic susceptibility measurements and thermogravimetric analyses (TGA).     

Thermal, spectral and magnetic characterization of Co(II), Ni(II) AND Cu(II) 4-chloro-2-nitrobenzoates

Physico-chemical properties of 4-chloro-2-nitrobenzoates of Co(II), Ni(II), and Cu(II) were studied. The complexes were obtained as mono- and trihydrates with a metal ion to ligand ratio of 1:2. All analysed 4-chloro-2-nitrobenzoates are polycrystalline compounds with colours depending on the central ions: pink for Co(II), green for Ni(II), and blue for Cu(II) complexes. Their thermal decomposition was studied only in the range of 293–523 K, because it was found that on heating in air above 523 K 4-chloro-2-nitrobenzoates decompose explosively. Hydrated complexes lose crystallization water molecules in one step and anhydrous compounds are formed. The final products of their decomposition are the oxides of the respective transition metals. From the results it appears that during dehydration process no transformation of nitro group to nitrite takes place. The solubilities of analysed complexes in water at 293 K are of the order of 10^–4–10^–2 mol dm^–3. The magnetic moment values of Co²⁺, Ni²⁺ and Cu²⁺ ions in 4-chloro-2-nitrobenzoates experimentally determined at 76–303 K change from 3.89 to 4.82 μ_B for Co(II) complex, from 2.25 to 2.98 μ_B for Ni(II) 4-chloro-2-nitrobenzoate, and from 0.27 to 1.44 μ_B for Cu(II) complex. 4-chloro-2-nitrobenzoates of Co(II), and Ni(II) follow the Curie–Weiss law. Complex of Cu(II) forms dimer.     

Polarized spectroscopy and hybrid materials of chiral Schiff base Ni(II), Cu(II), Zn(II) complexes with included or separated azo-groups

Chiral Schiff base complexes containing azo-groups, bis(N-R-1-naphtylethyl-4-phenyldiazenylsalicydenaminato) nickel(II), copper(II), and zinc(II) complexes affording a distorted square planar trans-[MN₂O₂] coordination geometry were prepared newly. Organic/inorganic hybrid materials in polymethylmethacrylate (PMMA) cast films of them (a containing type) or the analogous chiral Schiff base complexes, bis(N-R-1-phenylethyl-3,5-dichlorosalicydenaminato) nickel(II), copper(II), and zinc(II), and azobenzene (AZ) (a separated type) were assembled for comparison of polarized UV light induced molecular arrangement caused by Weigert effect. Investigation of parameters for optical anisotropy of metal complexes as well as AZ suggested that the degree of increasing optical anisotropy of the containing type is higher than that of the separated type based on π-π^∗ (of which characteristic band appeared around 380 nm), n-π^∗, and d-d bands of polarized absorption electronic spectra. Rigid nickel(II) or zinc(II) complexes are easy to increase optical anisotropy than flexible copper(II) complexes for both types.     

Bioactive Co(II), Ni(II), and Cu(II) Complexes Containing a Tridentate Sulfathiazole-Based (ONN) Schiff Base

New Co(II), Ni(II), and Cu(II) complexes were synthesized with the Schiff base ligand obtained by the condensation of sulfathiazole with salicylaldehyde. Their characterization was performed by elemental analysis, molar conductance, spectroscopic techniques (IR, diffuse reflectance and UV–Vis–NIR), magnetic moments, thermal analysis, and calorimetry (thermogravimetry/derivative thermogravimetry/differential scanning calorimetry), while their morphological and crystal systems were explained on the basis of powder X-ray diffraction results. The IR data indicated that the Schiff base ligand is tridentate coordinated to the metallic ion with two N atoms from azomethine group and thiazole ring and one O atom from phenolic group. The composition of the complexes was found to be of the [ML₂]∙nH₂O (M = Co, n = 1.5 (1); M = Ni, n = 1 (2); M = Cu, n = 4.5 (3)) type, having an octahedral geometry for the Co(II) and Ni(II) complexes and a tetragonally distorted octahedral geometry for the Cu(II) complex. The presence of lattice water molecules was confirmed by thermal analysis. XRD analysis evidenced the polycrystalline nature of the powders, with a monoclinic structure. The unit cell volume of the complexes was found to increase in the order of (2) < (1) < (3). SEM evidenced hard agglomerates with micrometric-range sizes for all the investigated samples (ligand and complexes). EDS analysis showed that the N:S and N:M atomic ratios were close to the theoretical ones (1.5 and 6.0, respectively). The geometric and electronic structures of the Schiff base ligand 4-((2-hydroxybenzylidene) amino)-N-(thiazol-2-yl) benzenesulfonamide (HL) was computationally investigated by the density functional theory (DFT) method. The predictive molecular properties of the chemical reactivity of the HL and Cu(II) complex were determined by a DFT calculation. The Schiff base and its metal complexes were tested against some bacterial strains (Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Bacillus subtilis). The results indicated that the antibacterial activity of all metal complexes is better than that of the Schiff base.     

The role of chiral dopants in organic/inorganic hybrid materials containing chiral Schiff base Ni(II), Cu(II) and Zn(II) complexes

Chiral Schiff base complexes containing azo-groups, bis(N-R-1-cyclohexylethyl-4-phenyldiazenylsalicydenaminato) nickel(II), copper(II) and zinc(II) complexes, and without azo-groups, bis(N-R-1-cyclohexylethyl-3,5-dichlorosalicydenaminato) nickel(II), copper(II) and zinc(II) complexes, affording a distorted square planar trans-[MN₂O₂] coordination geometry were prepared. Organic/inorganic hybrid materials in polymethylmethacrylate (PMMA) spincoat films of the complexes (both the azobenzene (AZ) containing type and the latter complexes of the AZ separated type) were assembled for a comparison of polarized UV light induced molecular arrangement caused by the Weigert effect. Investigation of the parameters for the optical anisotropy of the metal complexes as well as AZ suggested that the degree of increasing optical anisotropy of the containing type was higher than that of the separated type based on π-π^∗ (of which a characteristic band appeared around 380 nm) and n-π^∗ bands of polarized absorption electronic spectra. In the AZ containing type, the rigid nickel(II) or zinc(II) complexes easily increase the optical anisotropy compared to the flexible copper(II) complexes. In the AZ separated type, interestingly, enhancement of some CD bands suggests the role of chiral dopants of some complexes without azo-groups for AZ.     

Nickel(II), copper(II) and zinc(II) complexes withN-phenylglycine in water-methanol solution

The complex equilibria of the Ni(II), Cu(II), and Zn(II) complexes withN-phenylglycine have been studied by computer analysis of potentiometric data. The mode of coordination has been established by¹H NMR and IR studies.

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Nickel(II), Kupfer(II) und Zink(II)-Komplexe mitN-Phenylglycin in Wasser-Methanol-Lösung

Zusammenfassung Anhand der Computer-Analyse von potentiometrischen Daten wurden die Bildungsgleichgewichte von Nickel(II), Kupfer(II) und Zinc(II)-Komplexen mitN-Phenylglycin untersucht. Zur Bestätigung des Koordinationstyps wurden¹H-NMR- und IR-Messungen vorgenommen.

     

Studies on mononuclear chelates derived from substituted Schiff-base ligands (part 6): synthesis and characterization of a new 3-ethoxysalicyliden- p -aminoacetophenoneoxime and its complexes with cobalt(II), nickel(II), copper(II) and zinc(II)

Schiff-base complexes of cobalt(II), nickel(II), copper(II) and, zinc(II) with 3-ethoxysalicyliden-p-aminoacetophenoneoxime (HL) were prepared and characterized on the basis of elemental analyses, IR, ¹H- and ¹³C-NMR, electronic spectra, magnetic susceptibility measurements, molar conductivity and thermogravimetric analyses (TGA). A tetrahedral geometry has been assigned to the complexes.     

Synthesis and photoluminescent properties of a Schiff-base ligand and its mononuclear Zn(II), Cd(II), Cu(II), Ni(II) and Pd(II) metal complexes

Mononuclear Zn(II), Cd(II), Cu(II), Ni(II) and Pd(II) metal complexes of Schiff-base ligand(HL₁) derived from 8-acetyl-7-hydroxycoumarin and P-phenylenediamine were prepared and characterized by microanalytical, mass, UV–Vis, IR, ¹H NMR, ¹³C NMR, ESR, conductance and fluorescence studies. The measured low molar conductance values in DMSO indicate that the complexes are non-electrolytes. The structures of the solid complexes under study are established by using IR, electronic and ESR spectroscopy suggesting that Zn(II) and Ni(II) complexes are octahedral, Cd(II) complex is tetrahedral, Cu(II) and Pd(II) complexes are square planar. The ESR spectrum of the Cu(II) complex in DMSO at 298 and 150 K was recorded and its salient features are reported, it supports the mononuclear structure. The Schiff base exhibited photoluminescence originating from intraligand (π–π*) transitions. Metal-mediated enhancement is observed on complexation of HL with Zn(II) and Cd(II), whereas metal-mediated fluorescence quenching occurs in Cu(II), Ni(II) and Pd(II).     

Complexation of [S,S,S]- and [R,S,R]-isomers of N-bis [2-(1,2-dicarboxyethoxy)ethyl] aspartic acid with Mg(II), Ca(II), Mn(II), Fe(III), Cu(II) and Zn(II) ions in aqueous solution

In a search for environmentally friendly metal chelating ligands for industrial applications, the protonation and complex formation equilibria of [S,S,S]- and [R,S,R]-isomers of N-bis[2-(1,2-dicarboxyethoxy)ethyl] aspartic acid (BCA6) with Mg(II), Ca(II), Mn(II), Fe(III), Cu(II) and Zn(II) ions in aqueous 0.1 M NaCl solution were studied at 25°C by potentiometric titration. The model for complexation and the stability constants of the different complexes were determined for each metal ion using the computer program SUPERQUAD. With all metal ions (M ⁿ⁺), stable ML ^n?6 complexes dominated complex formation for both isomers. Differences in complexation models were found for binuclear species.     

Synthesis, crystal structure, spectroscopic and photoluminescence studies of manganese(II), cobalt(II), cadmium(II), zinc(II) and copper(II) complexes with a pyrazole derived Schiff base ligand

Varying coordination modes of the Schiff base ligand H₂L [5-methyl-1-H-pyrazole-3-carboxylic acid (1-pyridin-2-yl-ethylidene)-hydrazide] towards different metal centers are reported with the syntheses and characterization of four mononuclear Mn(II), Co(II), Cd(II) and Zn(II) complexes, [Mn(H₂L)(H₂O)₂](ClO₄)₂(MeOH) (1), [Co(H₂L)(NCS)₂] (2), [Cd(H₂L)(H₂O)₂](ClO₄)₂ (3) and [Zn(H₂L)(H₂O)₂](ClO₄)₂ (4), and a binuclear Cu(II) complex, [Cu₂(L)₂](ClO₄)₂ (5). In the complexes 1-4 the neutral ligand serves as a 3N,2O donor where the pyridine ring N, two azomethine N and two carbohydrazine oxygen atoms are coordinatively active, leaving the pyrazole-N atoms inactive. In the case of complex 5, each ligand molecule behaves as a 4N,O donor utilizing the pyridine N, one azomethine N, the nitrogen atom proximal to the azomethine of the remaining pendant arm and one pyrazole-N atom to one metal center and the carbohydrazide oxygen atom to the second metal center. The complexes 1-4 are pentagonal bipyramidal in geometry. In each case, the ligand molecule spans the equatorial plane while the apical positions are occupied by water molecules in 1, 3 and 4 and two N bonded thiocyanate ions in 2. In complex 5, the two Cu(II) centers have almost square pyramidal geometry (τ = 0.05 for Cu1 and 0.013 for Cu2). Four N atoms from a ligand molecule form the basal plane and the carbohydrazide oxygen atom of a second ligand molecule sits in the apex of the square pyramid. All the complexes have been X-ray crystallographically characterized. The Zn(II) and Cd(II) complexes show considerable fluorescence emission while the remaining complexes and the ligand molecule are fluorescent silent.     

Synthesis,characterization and fluorescence spectra of mixed ligand Zn(II), Cd(II) and Hg(II) complexes with 1,10-phenanthroline-5,6-dione ligand

The novel mixed ligand complexes [M(bpy)(phen-dione)](PF₆)₂ (M?=?Zn(II), Cd(II) and Hg(II), bpy?=?2,2^′-bipyridine and phen-dione?=?1,10-phenanthroline-5,6-dione) have been synthesized and characterized by elemental analysis, IR, ¹H NMR and electronic absorption spectroscopies. The ν(C=O) of coordinated phen-dione in these complexes are very similar to the free phen-dione ligand showing that phen-dione is not coordinated to metal ion from its C=O sites. Absorption spectra of the complexes show two absorption bands for intraligand transitions. These absorption bands show dependence to the dielectric constant of solvent. These complexes exhibit an intensive fluorescence band around 535?nm in DMF when the excitation wavelength is 260?nm at room temperature. The fluorescence intensity of these complexes is larger than that of the free ligand.     

Poly(propylene imine) dendrimer complexes of Cu(II), Zn(II), and Co(III) as catalysts of hydrolysis of p-nitrophenyl diphenyl phosphate

Poly(propylene imine) dendrimers having 8, 32, and 64 primary amine end groups form diamino Cu(II), diamino Zn(II), and tetramino Co(III) complexes that are identified spectrophotometrically and titrimetrically. The dendrimer–metal ion complexes catalyze the hydrolysis of p-nitrophenyl diphenyl phosphate in zwitterionic buffer solutions at pH ≤ 8.1 with relative activities Cu(II) > Zn(II) > Co(III). The rates of hydrolysis are faster with sodium perchlorate than with sodium chloride to control ionic strength. In sodium perchlorate solutions with Cu(II) the rates increase with increasing size of the dendrimer. In sodium chloride solutions with Cu(II) the rates decrease with increasing size of the dendrimer. Rate constants in buffered sodium chloride solutions of dendrimers and 1.0mM Cu(II) are 1.3–6.3 times faster than in the absence of Cu(II). The fastest hydrolyses occurred at a dendrimer primary amine to Cu(II) ratio NH₂/Cu ≤ 2. At NH₂/Cu = 4 and with the 1,4,7,10-tetraazacyclodecane complex of Cu(II) hydrolysis rates were much slower. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2727–2736, 1999     

Thermal, spectral and magnetic behaviour of 2,3,4-trimethoxybenzoates of Mn(II), Co(II), Ni(II) AND Cu(II)

Four new complexes of 2,3,4-trimethoxybenzoic acid anion with manganese(II), cobalt(II), nickel(II) and copper(II) cations were synthesized, analysed and characterized by standard chemical and physical methods. 2,3,4-Trimethoxybenzoates of Mn(II), Co(II), Ni(II) and Cu(II) are polycrystalline compounds with colours typical for M(II) ions. The carboxylate group in the anhydrous complexes of Mn(II), Co(II) and Ni(II) is monodentate and in that of Cu(II) monohydrate is bidentate bridging one. The anhydrous complexes of Mn(II), Co(II) and Ni(II) heated in air to 1273 K are stable up to 505–517 K. Next in the range of 505–1205 K they decompose to the following oxides: Mn₃O₄, CoO, NiO. The complex of Cu(II) is stable up to 390 K, and next in the range of 390–443 K it loses one molecule of water. The final product of its decomposition is CuO. The solubility in water at 293 K is of the order of 10^–3 mol dm^–3 for the Mn(II) complex and 10^–4 mol dm^–3 for Co(II), Ni(II) and Cu(II) complexes. The magnetic moment values of Mn²⁺, Co²⁺, Ni²⁺ and Cu²⁺ ions in 2,3,4-trimethoxybenzoates experimentally determined in the range of 77–300 K change from 5.64–6.57 μB (for Mn²⁺), 4.73–5.17 μB (for Co²⁺), 3.26–3.35 μB (for Ni²⁺) and 0.27–1.42 μB (for Cu²⁺). 2,3,4-Trimethoxybenzoates of Mn(II), Co(II) and Ni(II) follow the Curie–Weiss law, whereas that of Cu(II) forms a dimer.     

Photofunctional supramolecular solution systems of chiral Schiff base nickel(II), copper(II), and zinc(II) complexes and photochromic azobenzenes

Preparations, crystal structures, electronic and CD spectra are reported for new chiral Schiff base complexes, bis(N-R-1-naphthylethyl-3,5-dichlorosalicydenaminato)nickel(II), copper(II), and zinc(II). Nickel(II) and copper(II) complexes adopt a square planar trans-[MN₂O₂] coordination geometry with Δ(R,R) configuration. While zinc(II) complex adopts a compressed tetrahedral trans-[MN₂O₂] one with Δ(R,R) configuration and exhibits an emission band around 21 000 cm⁻¹ (λ_ex = 27 000 cm⁻¹). Absorption and CD spectra were recorded in N,N′-dimethylformamide, acetone, methanol, chloroform, and toluene solutions to discuss relationships between spectral shifts of d–d and π–π^∗ bands by structural changes of the complexes and physical properties of the solvents. Moreover, we have attempted to investigate conformational changes of the complexes induced by photoisomerization of azobenzene, 4-hydroxyazobenzene, or 4-aminoazobenzene, in various solutions under different conditions. Weak intermolecular interactions between complexes and azobenzenes are important for the phenomenon by conformational changes of bulky π-conjugated moieties of the ligands.     

四氮大环-金属配合物与DNA作用的电化学及谱学研究

Mononuclear copper（Ⅱ）, nickel（Ⅱ） and cobalt（Ⅲ） tetracoordinate macrocyclic complexes were synthesized and spectroscopically characterized. The crystal structure of the three compounds were determined by X-ray crystallography. The electrochemical experimental results indicate that the three complexes could interact with DNA mainly by electrostatic interaction. The interaction of tetracoordinate macrocyclic cobalt（Ⅲ） complex with DNA was studied by cyclic voltammetry and UV-vis spectroscopy. The experimental results reveal that tetracoordinate macrocyc- lic cobalt（Ⅲ） complex could interact with DNA by electrostatic interaction to form a 1 ： 1 DNA association complex with a binding constant of 7.50 ×10^3 L·mol^-1.     

Application of Multivariate Calibration Methods for the Simultaneous Multiwavelength Spectrophotometric Determination of Fe(II), Cu(II), Zn(II), and Mn(II) in Mixtures

Abstract

A sensitive method for the simultaneous spectrophotometric determination of Fe(II), Cu(II), Zn(II), and Mn(II) in mixtures has been developed with the aid of multivariate calibration methods, such as classical least squares (CLS), principal component regression (PCR) and partial least squares (PLS). The method is based on the spectral differences of the analytes in their complexation reaction with 4‐(2‐pyridylazo)‐resorcinol (PAR) and the use of full spectra with wavelengths in the range of 300–600 nm. It was found that both the spectral positive and negative bands obtained against the PAR blank, are proportional to the concentration for each metal complex. The obtained linear calibration concentration ranges are 0.025–0.6, 0.05–0.8, 0.025–0.8, and 0.05–0.8 µg ml^?1 for Fe(II), Cu(II), Zn(II), and Mn(II), respectively, and the LODs for the four metal ions were found to be approximately 1–3×10^?2 µg ml^?1. The proposed method was applied to a verification set of synthetic mixtures of these four metal ions, with models built in three different wavelength ranges, i.e., 300–450, 450–600, and 300–600 nm, corresponding to the positive, negative bands and their combinations, respectively. It was shown that the PLS model for the 300–600 nm range gave the best results (RPE_T=6.9% and average recovery ～100%; cf. PCR: RPE_T=9.5% and average Recovery ～110%). This method was also successfully applied for the determination of the four metal ions in pharmaceutical preparations, chicken feedstuff, and water samples.