Cd Sites Research Articles

Endoglucanase Peripheral Loops Facilitate Complexation of Glucan Chains on Cellulose via Adaptive Coupling to the Emergent Substrate Structures

We examine how the catalytic domain of a glycoside hydrolase family 7 endoglucanase catalytic domain (Cel7B CD) facilitates complexation of cellulose chains from a crystal surface. With direct relevance to the science of biofuel production, this problem also represents a model system of biopolymer processing by proteins in Nature. Interactions of Cel7B CD with a cellulose microfibril along different paths of complexation are characterized by mapping the atomistic fluctuations recorded in free-energy simulations onto the parameters of a coarse-grain model. The resulting patterns of protein-biopolymer couplings also uncover the sequence signatures of the enzyme in peeling off glucan chains from the microfibril substrate. We show that the semiopen active site of Cel7B CD exhibits similar barriers and free energies of complexation over two distinct routes; namely, scooping of a chain into the active-site cleft and threading from the chain end into the channel. On the other hand, the complexation energetics strongly depends on the surface packing of the targeted chain and the resulting interaction sites with the enzyme. A revealed principle is that Cel7B CD facilitates cellulose deconstruction via adaptive coupling to the emergent substrate. The flexible, peripheral segments of the protein outside of the active-site cleft are able to accommodate the varying features of cellulose along the simulated paths of complexation. The general strategy of linking physics-based molecular interactions to protein sequence could also be helpful in elucidating how other protein machines process biopolymers.

Low-Temperature Photoluminescence Study of CdTe:In Crystals Annealed in Molten Bismuth

We used a low-temperature photoluminescence (PL) technique to investigate CdTe:In crystals after annealing in molten bismuth (Bi). The two annealed samples showed different resistivities after the treatment. For both samples, we observed very strong emissions in the excitonic spectral region and revealed fine structures of exciton emissions in the PL spectrum. In the sample with high resistivity, we found one ionized donor-bound exciton peak, (D+,X), that we ascribed to incorporated Bi atoms occupying Cd sites in the CdTe. The temperature dependence of the (D+,X) peak emission had an associated activation energy of 3.59 meV for the exciton bound to this ionized donor. Meanwhile, a donor–acceptor pair peak at 1.5315 eV, which was absent from the PL of the low-resistivity sample, suggested the likelihood of some Bi atoms occupying Te sites in the high-resistivity sample. Our findings highlight the need for detailed investigation of annealing conditions to ensure precise control of the electrical properties of the material during annealing in molten Bi.

Removal of Cd(II) ions from aqueous solutions, by adsorption onto Junipers Procera Roots

This study explored the adsorption behavior of Cd(II) ions on Junipers Procera Roots powder from aqueous solutions. The effect of various operational parameters such as pH, contact time, initial adsorbate concentration, dosage of adsorbent and temperature on adsorption of Cd(II) ions were investigated using batch adsorption experiments. The optimum pH for Cd(II) adsorption was found to be 7.0. The suitability of Langmuir and Freundlich adsorption models to the equilibrium data was investigated. The adsorption was well described by the Freundlich isotherm model indicating the presence of heterogeneous sites for Cd(II) adsorption. Thermodynamic parameters showed that the adsorption of Cd(II) on Junipers Procera Roots was feasible, spontaneous and exothermic.

Metal–insulator transition in Na-doped post-spinel CdRh2O4

Na doping of post-spinel CdRh2O4 was achieved over the full composition range to NaRh2O4 using high-pressure and high-temperature synthesis conditions. X-ray diffraction analysis confirmed that Na occupies the Cd site and that the host structure is retained, in sharp contrast to what was observed for spinel CdRh2O4, where Na was not accommodated at all. As the Na content was increased, the electrically insulating state changed to a conducting state at a critical composition close to x=0.75 in Cd1−xNaxRh2O4. The specific heat data confirm that the density of electronic states at the Fermi level was enhanced around this composition, suggesting that the metal–insulator transition is likely induced by band filling. In addition, unusual antiferromagnetism was observed in several compounds with intermediate Na concentrations, and this phenomenon was seemingly independent of the metal–insulator transition.

Pirquitasite, Ag2ZnSnS4

Pirquitasite, ideally Ag2ZnSnS4 (disilver zinc tin tetra­sulfide), exhibits tetra­gonal symmetry and is a member of the stannite group that has the general formula A2BCX 4, with A = Ag, Cu; B = Zn, Cd, Fe, Cu, Hg; C = Sn, Ge, Sb, As; and X = S, Se. In this study, single-crystal X-ray diffraction data are used to determine the structure of pirquitasite from a twinned crystal from the type locality, the Pirquitas deposit, Jujuy Province, Argentina, with anisotropic displacement parameters for all atoms, and a measured composition of (Ag1.87Cu0.13)(Zn0.61Fe0.36Cd0.03)SnS4. One Ag atom is located on Wyckoff site Wyckoff 2a (symmetry -4..), the other Ag atom is statistically disordered with minor amounts of Cu and is located on 2c (-4..), the (Zn, Fe, Cd) site on 2d (-4..), Sn on 2b (-4..), and S on general site 8g. This is the first determination of the crystal structure of pirquitasite, and our data indicate that the space group of pirquitasite is I-4, rather than I-42m as previously suggested. The structure was refined under consideration of twinning by inversion [twin ratio of the components 0.91 (6):0.09 (6)].

Biosorption properties of Cd(II), Pb(II), and Cu(II) of extracellular polymeric substances (EPS) extracted from Aspergillus fumigatus and determined by polarographic method

Extracellular polymeric substances (EPS) were extracted from Aspergillus fumigatus using cationic exchange resin technique. The EPS were mainly composed of polysaccharide and low quantities of protein and nucleic acid. Biosorption of Cd(II), Pb(II), and Cu(II) of EPS was investigated as a function of pH using differential pulse polarography and the Ruzic model. Results showed that the EPS biosorption capacity determined using either the direct titration curves i = f(C M) or the method proposed by Ruzic (Analytica Chimica Acta 140:99-113, 1982) were coincident. Cu(II) had the highest affinity with EPS followed by Pb(II) and Cd(II). The total number of binding sites for Cu(II) and Cd(II) increased with pH in the range of 4.0-7.0. Similar trend was observed for Pb(II) at pH 4.0-5.0, while precipitates were observed at pH 6.0 and 7.0. The conditional binding constants of these three metals displayed low levels of fluctuation with pH and ranged from 4.02 ± 0.02 to 5.54 ± 0.05.

Five-coordinate Cd in the crystal structure of triploidite-type Cd2(AsO4)(OH)

This paper reports on hydrothermal synthesis and crystal structure refinement of dicadmium arsenate hydroxide, Cd2(AsO4)(OH), obtained at 220 °C and autogenous pressure. Its crystal structure is monoclinic, space group P21/a, with a = 13.097(3), b = 14.089(3), c = 10.566(2) A, β = 108.38(3)°, V = 1850.2(6) A3 (Z = 16). It is isotypic with the members of the triploidite group of minerals and synthetic compounds, and thus shows a close topological relationship with the triplite group. The complex framework contains edge- and corner-sharing CdO4(OH) and CdO4(OH)2 polyhedra, linked via corner-sharing to AsO4 tetrahedra (average As—O distances range between 1.682 and 1.688 A). Four five-coordinated Cd sites are at the centers of distorted trigonal bipyramids (average Cd—O distances are between 2.225 and 2.251 A), whereas the remaining four Cd sites have a distorted octahedral coordination environment (average Cd—O distances are between 2.297 and 2.320 A). The positions of all the hydrogen atoms were located in a difference-Fourier map and refined with an isotropic displacement parameter. The hydrogen-bonds are weak to very weak. The unusual five-coordination of Cd is briefly discussed in relation to comparable minerals and compounds. Among triploidite-type compounds, Cd2(AsO4)(OH) is the member with the largest unit cell reported so far, and the second known arsenate member.

Use of (113)Cd NMR to probe the native metal binding sites in metalloproteins: an overview.

Our laboratories have actively published in this area for several years and the objective of this chapter is to present as comprehensive an overview as possible. Following a brief review of the basic principles associated with (113)Cd NMR methods, we will present the results from a thorough literature search for (113)Cd chemical shifts from metalloproteins. The updated (113)Cd chemical shift figure in this chapter will further illustrate the excellent correlation of the (113)Cd chemical shift with the nature of the coordinating ligands (N, O, S) and coordination number/geometry, reaffirming how this method can be used not only to identify the nature of the protein ligands in uncharacterized cases but also the dynamics at the metal binding site. Specific examples will be drawn from studies on alkaline phosphatase, Ca(2+) binding proteins, and metallothioneins.In the case of Escherichia coli alkaline phosphatase, a dimeric zinc metalloenzyme where a total of six metal ions (three per monomer) are involved directly or indirectly in providing the enzyme with maximal catalytic activity and structural stability, (113)Cd NMR, in conjunction with (13)C and (31)P NMR methods, were instrumental in separating out the function of each class of metal binding sites. Perhaps most importantly, these studies revealed the chemical basis for negative cooperativity that had been reported for this enzyme under metal deficient conditions. Also noteworthy was the fact that these NMR studies preceded the availability of the X-ray crystal structure.In the case of the calcium binding proteins, we will focus on two proteins: calbindin D(9k) and calmodulin. For calbindin D(9k) and its mutants, (113)Cd NMR has been useful both to follow actual changes in the metal binding sites and the cooperativity in the metal binding. Ligand binding to calmodulin has been studied extensively with (113)Cd NMR showing that the metal binding sites are not directly involved in the ligand binding. The (113)Cd chemical shifts are, however, exquisitely sensitive to minute changes in the metal ion environment.In the case of metallothionein, we will reflect upon how (113)Cd substitution and the establishment of specific Cd to Cys residue connectivity by proton-detected heteronuclear (1)H-(113)Cd multiple-quantum coherence methods (HMQC) was essential for the initial establishment of the 3D structure of metallothioneins, a protein family deficient in the regular secondary structural elements of α-helix and β-sheet and the first native protein identified with bound Cd. The (113)Cd NMR studies also enabled the characterization of the affinity of the individual sites for (113)Cd and, in competition experiments, for other divalent metal ions: Zn, Cu, and Hg.

Two‐Step Synthesis of a Novel Cd17 Sulfide Cluster through Ionic Clusters

AbstractA novel discrete neutral Cd17 sulfide cluster (denoted CMM‐9) with seven corners has been synthesized by slow diffusion of methanol into a mixed solution (DMF/CS2 = 1:1, weight ratio) containing an ionic starting material CMM‐4. The structures of CMM‐4 and CMM‐9 are determined from single crystal X‐ray diffraction data collected at 150 K. The structure of the new Cd17 cluster is distinctly different from the well‐known C1 cluster that also has 17 Cd sites. The UV/Vis spectrum of the new cluster CMM‐9 revealed a maximum absorption at 305 nm in DMF solution, which is slightly red‐shifted compared to the regular C1 cluster (C1, [Cd17S4(SPh)28]2–, with a maximum absorption at 296 nm).

Nitric oxide synthesis by bacterial cytochrome cd1 nitrite reductases

Cytochrome cd 1 nitrite reductase ( cd 1 NIR) is a haem-containing enzyme responsible for the reduction of nitrite into nitric oxide (NO), a key step in the bacterial anaerobic respiratory process of denitrification. The active site of cytochrome cd 1 contains the unique d 1 -haem cofactor, from which NO must be released. In general, reduced haems bind NO tightly relative to oxidised haems. The mechanism of NO release employed by cd 1 NiRs has been recently outlined, highlighting the essential role of the peculiar d 1 -haem, whose presence in these enzymes was largely unexplained. Briefly, we have shown that cd 1 NiRs can release quite rapidly the NO bound to the reduced d 1 haem. This finding challenged the classical idea that NO is often an “irreversible” inhibitor of reduced hemoproteins and prompted new studies on the reactivity of ferrous d 1 haem with NO, indicating that the d 1 haem has evolved to have low affinity for NO, as compared to other ferrous haems.

Rational design of a nitrite reductase based on myoglobin: a molecular modeling and dynamics simulation study

Myoglobin (Mb) is an ideal scaffold protein for rational protein design mimicking native enzymes. We recently designed a nitrite reductase (NiR) based on sperm whale Mb by introducing an additional distal histidine (Leu29 to His29 mutation) and generating a distal tyrosine (Phe43 to Tyr43 mutation) in the heme pocket, namely L29H/F43Y Mb, to mimic the active site of cytochrome cd (1) NiR from Ps. aeruginosa that contains two distal histidines and one distal tyrosine. The molecular modeling and dynamics simulation study herein revealed that L29H/F43Y Mb has the necessary structural features of native cytochrome cd (1) NiR and can provide comparable interactions with nitrite as in native NiRs, which provides rationality for the protein design and guides the protein engineering. Additionally, the present study provides an insight into the relatively low NiR activity of Mb in biological systems.

Reactions of cadmium(ii) nitrate with 4-(trimethylammonio)benzenethiolate in the presence of N-donor ligands

Reactions of Cd(NO(3))(2)·4H(2)O with TabHPF(6) (TabH = 4-(trimethylammonio)benzenethiol) and Et(3)N in the presence of NH(4)SCN and five other N-donor ligands such as 2,2'-bipyridine (2,2'-bipy), phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (2,9-dmphen), 2,6-bis(pyrazd-3-yl)pyridine (bppy) and 2,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)pyridine (bdmppy) gave rise to a family of Cd(II)/thiolate complexes of N-donor ligands, {[Cd(2)(μ-Tab)(4)(NCS)(2)](NO(3))(2)·MeOH}(n) (1), [Cd(2)(μ-Tab)(2)(L)(4)](PF(6))(4) (2: L = 2,2'-bipy; 3: L = phen), [Cd(Tab)(2)(L)](PF(6))(2) (4: L = 2,9-dmphen; 5: L = bppy), and [Cd(2)(μ-Tab)(2)(Tab)(2)(bdmppy)](2)(PF(6))(8)·H(2)O (6·H(2)O). These compounds were characterized by elemental analysis, IR spectra, UV-Vis spectra, (1)H NMR, electrospray ionization (ESI) mass spectra and single-crystal X-ray diffraction. For 1, each [Cd(NCS)](+) fragment is connected to its equivalents via a pair of Tab bridges to a one-dimensional chain. For 2 and 3, two [Cd(2,2'-bipy)(2)](2+) or [Cd(phen)(2)](2+) units are linked by a pair of Tab bridges to form a cationic dimeric structure. The Cd atom in [Cd(Tab)(2)(L)](2+) dication of 4 or 5 is coordinated by two Tab ligands and chelated by two N atoms from 2,9-dmphen (4) or three N atoms from bppy (5), forming a distorted tetrahedral (4) or trigonal bipyramidal (5) coordination geometry. For 6, each of two [Cd(Tab)(bdmppy)] fragments is linked to one [(Tab)Cd(μ-Tab)(2)Cd(Tab)] fragment via two Tab bridges to generate a unique cationic zigzag tetrameric structure where the Cd centers take a tetrahedral or a trigonal bipyramidal coordination geometry. The results may provide an interesting insight into mimicking the coordination spheres of the Cd(II) sites of metallothioneins and their interactions with various N-donor ligands encountered in nature.

Mechanism for suppression of ferroelectricity in Cd1−xCaxTiO3

A mechanism for cation-substitution-induced suppression of ferroelectricity in a perovskite-type ferroelectric oxide, CdTiO${}_{3}$, has been elucidated in terms of the relationship between the covalency and the lattice dynamics. Raman scattering experiments and first-principles calculations clarified that a change in the covalency of Cd sites due to Ca substitution selectively decreases the frequencies of the modes associated with octahedral rotations whose axes are perpendicular to the spontaneous polarization direction. The resulting destabilization of zigzag octahedral chains synchronizes the hardening of the ferroelectric soft mode, which suppresses the ferroelectricity. This result enhances our understanding of the relationship between local chemical bonds and macroscopic ferroelectricity.

Modeling metal bioaccumulation in the invasive mussels Dreissena polymorpha and Dreissena rostriformis bugensis in the rivers Rhine and Meuse

The metal-specific covalent index and the species-specific size-based filtration rate were integrated into a biokinetic model estimating metal bioaccumulation in mussels from the dissolved phase and phytoplankton. The model was validated for zebra (Dreissena polymorpha) and quagga (Dreissena rostriformis bugensis) mussels in the rivers Rhine and Meuse, the Netherlands. The model performed well in predicting tissue concentrations in different-sized zebra mussels from various sampling sites for (55) Mn, (56) Fe, (59) Co, (60) Ni, (82) Se, (111) Cd, (118) Sn, and (208) Pb (r(2) =0.71-0.99). Performance for (52) Cr, (63) Cu, (66) Zn, (68) Zn, and (112) Cd was moderate (r(2) <0.20). In quagga mussels, approximately 73 to 94% of the variability in concentrations of (82) Se, (111) Cd, (112) Cd, and (208) Pb was explained by the model (r(2) =0.73-0.94), followed by (52) Cr, (55) Mn, (56) Fe, (60) Ni, and (63) Cu (r(2) =0.48-0.61). Additionally, in both zebra and quagga mussels, average modeled concentrations were within approximately one order of magnitude of the measured values. In particular, in zebra mussels, estimations of (60) Ni and (82) Se concentrations were equal to 51 and 76% of the measurements, respectively. Higher deviations were observed for (52) Cr, (59) Co, (55) Mn, (56) Fe, (111) Cd, (63) Cu, and (112) Cd (underestimation), and (66) Zn, (68) Zn, (208) Pb, and (118) Sn (overestimation). For quagga mussels, modeled concentrations of (66) Zn and (68) Zn differed approximately 14% from the measured levels. Differences between predictions and measurements were higher for other metals.

Ab-initio investigations of structural, electronic, magnetic and optical properties of ferromagnetic Cd 1– xMn xTe

We report ab-initio calculations of the structural, electronic, magnetic and optical properties of the alloy Cd 1– x Mn x Te as a function of the Mn concentration ‘ x’. Ab-initio calculations are based on the density functional theory (DFT) within the generalized gradient approximation (GGA). The calculated lattice constants of the Cd 1– x Mn x Te alloys exhibit Vegard's law downward bowing parameter. For the minority spin channel the Fermi level shifts toward higher energy with the value of ‘ x’ in Cd 1– x Mn x Te. The spin-exchange splitting energy Δ x (d) increases with increasing ‘ x’ in Cd 1– x Mn x Te and the values of p–d exchange splitting energy Δ x (pd) of Cd 1– x Mn x Te show that the effective potential for the minority spin is more attractive than that for the majority spin. The values of exchange constants N 0 α and N 0 β obtained for Cd 1– x Mn x Te are in agreement with the reported data. The magnetic moment per Mn atom reduces from its free space charge value of 5μ B to around 4μ B due to p–d hybridization and this results into an appearance of small local magnetic moments on the non-magnetic Cd and Te sites. The absorption threshold shifts toward higher energy and the static refractive index decreases with the increasing value of ‘ x’ in Cd 1– x Mn x Te.

Electric field gradient at the 111Cd(←111In) site in Ga-doped ZnO

Abstract The time-differential perturbed angular correlation (TDPAC) method was applied to a study of the local environment at the 111Cd(←111In) probe nucleus introduced in 0.5 at. % Ga-doped ZnO. The TDPAC spectrum obtained at room temperature suggests that the doped Ga ions reside at the substitutional Zn site and they are locally associated in immediate proximity to the probe, reflecting strong attractive force between the probe and the dopants. The relative width of the magnitude of the electric field gradient produced at the probe nucleus shows that the doped Ga ion(s) adjacent to the probe is/are diversely distributed compared with doped In ion(s).

Characterization of Primary Amine Capped CdSe, ZnSe, and ZnS Quantum Dots by FT-IR: Determination of Surface Bonding Interaction and Identification of Selective Desorption

Surface ligands of semiconductor quantum dots (QDs) critically influence their properties and functionalities. It is of strong interest to understand the structural characteristics of surface ligands and how they interact with the QDs. Three quantum dot (QD) systems (CdSe, ZnSe, and ZnS) with primary aliphatic amine capping ligands were characterized primarily by FT-IR spectroscopy as well as NMR, UV-vis, and fluorescence spectroscopy, and by transmission electron microscopy (TEM). Representative primary amines ranging from 8 to 16 carbons were examined in the vapor phase, KBr pellet, and neat and were compared to the QD samples. The strongest hydrogen-bonding effects of the adsorbed ligands were observed in CdSe QDs with the weakest observed in ZnS QDs. There was an observed splitting of the N-H scissoring mode from 1610 cm(-1) in the neat sample to 1544 and 1635 cm(-1) when bound to CdSe QDs, which had the largest splitting of this type. The splitting is attributed to amine ligands bound to either Cd or Se surface sites, respectively. The effect of exposure of the QDs dispersed in nonpolar medium to methanol as a crashing agent was also examined. In the CdSe system, the Cd-bound scissoring mode disappeared, possibly due to methanol replacing surface cadmium sites. The opposite was observed for ZnSe QDs, in which the Se-bound scissoring mode disappeared. It was concluded that surface coverage and ligand bonding partners could be characterized by FT-IR and that selective removal of surface ligands could be achieved through introduction of competitive binding interactions at the surface.

Application of structural analogs of dimercaptosuccinic acid-functionalized silica nanoparticles (DMSA-[silica]) to adsorption of mercury, cadmium, and lead

In order to gain additional insight into mercury selectivity with nano-sized DMSA-[silica], we investigated a series of ligands related to DMSA, these are: monomercaptosuccinic acid; MMSA, 2-mercapto-4-methyl-5-thiazoleacetic acid; MCT, ortho-thiosalicylic acid; o-TSA and para-thiosalicylic acid; p-TSA. The MMSA chelate is structurally similar to DMSA except that it has only one thiol group. The chelates o-TSA and p-TSA each have one thiol and one carboxylic acid group. MCT includes neutral S and N atoms in close proximity to the thiolate binding site. MCT, o-TSA and p-TSA resemble each other in having equal numbers of carboxylic acid and thiol groups and formation of amide bonds with the linker on silica is expected to eliminate the carboxylate binding sites, making thiolates the only binding sites for Hg(II), Cd(II), and Pb(II) metals ions in the nano-sized; MMSA-[silica], MCT-[silica], o-TSA-[silica], and p-TSA-[silica]. Each of the nano-sized MMSA-[silica], MCT-[silica], o-TSA-[silica], and p-TSA-[silica], show a higher preference for Hg(II) over Cd(II) and Pb(II) compared to the same free chelates in solution, respectively. In addition, there are differences in the level of metal ion chelation for each functionalized silica nanoparticle. These differences in the degree of metal chelation for each functionalized silica nanoparticles surface are explained by the difference in thiolate/carboxylate ratio upon attachment to the surface and on steric reasons based on the orientation of the thiol groups on the surface. When attached via amide bond formation, the thiolate site in o-TSA-[silica] will face towards the silica surface, while for p-TSA-[silica], the thiolate site is expected to be pointed outwards and away from the silica surface. In comparing MMSA-[silica] to DMSA-[silica], the thiolate/carboxylate ratio decreases from 2/1 in DMSA-[silica] to 1/1 in MMSA-[silica] (assuming attachment via one amide bond in each case). This effect of increasing the ratio of thiolate to carboxylate upon attachment to the surface is believed to play a role in the selectivity enhancement towards Hg(II) over Cd(II) and Pb(II).

First principles study of half-metallic ferromagnetism in Cr-doped CdTe

We report a systematic study of the structural, electronic and magnetic properties of Cr-doped CdTe for various Cr concentrations x (=0.25, 0.5, 0.75 and 1.0) using first principles calculations based on the density functional theory (DFT). The electronic band structure of the alloy has been calculated using the Wu–Cohen (WC) as well as the Angel-Vosko (EV) generalized gradient approximation (GGA) for the exchange-correlation potential. The analysis of the density of states (DOS) curves shows the half-metallic ferromagnetic character with half-metallic gap more than 0.52 eV. While the origin of half-metallic ferromagnetism is explained, the band structure calculations are used to determine s ( p) –d exchange constants N 0 α (conduction band) and N 0 β (valence band) that agree with typical magneto-optical experiment. It is found that the p–d hybridization reduces the magnetic moment of Cr from its free space charge value and produces small magnetic moments on the Cd and Te sites. Lastly, we discuss the robustness of half-metallicity with respect to the variation of lattice constants of the Cr x Cd 1− x Te alloys.

The –Cys–Cys– motif in Helicobacter pylori's Hpn and HspA proteins is an essential anchoring site for metal ions

The Hpn and HspA proteins from H. pylori are significant for nickel homeostasis and protect the cells from higher concentrations of external metal ions. Both proteins have a unique histidine- and cysteine-rich domain at the C terminus. The interactions of Ni(2+), Bi(3+), Zn(2+) and Cd(2+) ions with C-terminal Ac-CCSTSDSHHQ-NH(2) and Ac-EEGCCHGHHE-NH(2) fragments from Hpn and the Ac-GSCCHTGNHD-NH(2) sequence from HspA were studied by potentiometry, mass spectrometry, circular dichroism and UV-Vis spectroscopy. Ac-CC-NH(2) was used as a reference peptide. The studies have shown that nickel ions form planar complexes with a {2S(-),N(-)} binding mode. The thiol sulfurs of the -Cys-Cys- motif are also the anchoring sites for Bi(3+), Zn(2+) and Cd(2+) ions. The studied protein fragments have the highest affinity for Bi(3+) ions. The thermodynamic stability of Ni(2+) is much higher then that of Zn(2+).