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PubMed1999

Comparison of Heteronuclear Coupling Constants for Isostructural Nitrogen Coordination Compounds of (111/113)Cd and (199)Hg.

The complexation of Cd(II) by the tripodal ligand tris[(2-pyridyl)methyl]amine and dipodal ligand bis[(2-pyridyl)methyl]amine was investigated by solution-state NMR and X-ray crystallography. Cadmium coordination compounds exhibiting rarely observed solution-state NMR (1)H-(111/113)Cd satellites were characterized. The eight-coordinate complex [Cd(TMPA)(2)](ClO(4))(2).toluene (1) crystallizes in the triclinic space group P1 with a = 9.629(2) Å, b = 11.020(2) Å, c = 11.641(2) Å, alpha = 114.069(13) degrees, beta = 97.492(13) degrees, gamma = 91.034(14) degrees, and Z = 1. The average Cd-N(amine) distance is 2.53(4) Å and the average Cd-N(pyridyl) distance is 2.54(6) Å. The complex [Cd(BMPA)(NCCH(3))(OH(2))(OClO(3))][Cd(BMPA)(2)](ClO(4))(3).(CH(3)CN) (2) crystallizes in the triclinic space group P&onemacr; with a = 10.446(2) Å, b = 16.653(3) Å, c = 17.736(3) Å, alpha = 62.479(9) degrees, beta = 80.606(14) degrees, gamma = 84.66(2) degrees, and Z = 2. In the pseudo-octahedral monocation, the nitrogen-containing ligands occupy equatorial positions with Cd-N distances of 2.321(8), 2.283(7), and 2.263(8) Å for the amine, pyridyl (average) and acetonitrile nitrogens, respectively. Significant axial interactions occur with Cd-O bond distances of 2.313(7) Å (water) and 2.478(7) Å (perchlorate). In the pseudo-trigonal prismatic dication, the average Cd-N(amine) distances is 2.395(5) Å and the average Cd-N(pyridyl) distance is 2.362(8) Å. The solid-state structures and solution-state NMR trends were very similar to recently reported isovalent complexes of Hg(II), providing an exceptional opportunity to compare coupling constants of coordination compounds. Implications for the use of (111/113)Cd and (199)Hg NMR as metallobioprobes are discussed.

Journal Article↗
PubMed1997

Low levels of cadmium chloride damage the corneal endothelium.

The effect of cadmium chloride on the integrity of the endothelium of isolated bullfrog (Rana catesbeiana) corneas was examined by spectrophotometric analysis of corneal uptake of the vital stain Janus green and by scanning electron microscopy (SEM). The uptake of Janus green by the endothelium was dose related between 1.0 and 100.0 microM CdCl2. The effect of cadmium was significantly attenuated by the calcium channel blocker SKF 96365 and was augmented by the calcium ionophore A23187, indicating that cadmium influx through calcium channels is an important determinant of its cellular effect. The effect of cadmium was not altered by changes in the external calcium concentration, indicating that the mechanism does not involve competitive inhibition by calcium. SEM demonstrated significant structural damage to the corneal endothelium exposed to cadmium chloride, including focal disruption and denuding of the apical endothelial membrane.

Animals↗
PubMed2005

(CdSe)ZnS quantum dots and organophosphorus hydrolase bioconjugate as biosensors for detection of paraoxon.

In this paper, we first report a novel biosensor for the detection of paraoxon based on (CdSe)ZnS core-shell quantum dots (QDs) and an organophosphorus hydrolase (OPH) bioconjugate. The OPH was coupled to (CdSe)ZnS core-shell QDs through electrostatic interaction between negatively charged QDs surfaces and the positively charged protein side chain and ending groups (-NH2). Circular dichroism (CD) spectroscopy showed no significant change in the secondary structure of OPH after the bioconjugation, which indicates that the activity of OPH was preserved. Detectable secondary structure changes were observed by CD spectroscopy when the OPH/QDs bioconjugate was exposed to organophosphorus compounds such as paraoxon. Photoluminescence (PL) spectroscopic study showed that the PL intensity of the OPH/QDs bioconjugate was quenched in the presence of paraoxon. The overall quenching percentage as a function of paraoxon concentration matched very well with the Michaelis-Menten equation. This result indicated that the quenching of PL intensity was caused by the conformational change in the enzyme, which is confirmed by CD measurements. The detection limit of paraoxon concentration using OPH/QDs bioconjugate was about 10(-8) M. Although increasing the OPH molar ratio in the bioconjugates will slightly increase the sensitivity of biosensor, no further increase of sensitivity was achieved when the molar ratio of OPH to QDs was greater than 20 because the surface of QDs was saturated by OPH. These properties make the OPH/QDs bioconjugate a promising biosensor for the detection of organophosphorus compounds.

Aryldialkylphosphatase↗
PubMed2006

In vitro free radical scavenging activity of hepatic metallothionein induced in an Indian freshwater fish, Channa punctata Bloch.

Mammalian metallothioneins (MT) have been reported to scavenge free radicals. There is no experimental evidence to show that fish MT has a similar property. In the present study cadmium-induced MT (Cd-MT) from the liver of an Indian freshwater fish Channa punctata Bloch was investigated for its free radical scavenging activity using three different in vitro assays. Exposure to cadmium chloride (0.2 mg/kg body weight; three doses on alternate days) resulted in a marked induction of Cd-MT in liver. Only a single isoform of Cd-MT was found to be induced. Molecular weight of Cd-MT was found to be 14 kDa as deduced by SDS-PAGE analysis. The purified Cd-MT effectively scavenged the following free radicals: superoxide radical (O2*-), 2,2'-azinobis 3-ethylbenzothiazoline-6-sulfonic acid (ABTS*+) and 1,1-diphenyl-picrylhydrazyl radical (DPPH*). The radical scavenging effect was found to be concentration-dependent. Also, the purified MT exhibited an inhibitory effect on ferric nitrilotriacetate (Fe-NTA) induced oxidative DNA damage in vitro. The cysteine residues of MT are proposed to be the main candidate for its radical scavenging activity. Findings of the present study strongly suggest a free radical scavenging role for fish MT. Present study adds to the little existing knowledge about fish MT and its possible biological functions.

Animals↗
PubMed1990

Diamide reduces cadmium accumulation by human lung carcinoma A549 cells.

Human lung carcinoma A549-T27 cells were used to determine the effect of diamide on cadmium accumulation. Treatment of the cells with diamide decreased their cellular glutathione content to 51.6 +/- 7% of control and significantly decreased their cadmium accumulation both as a function of time and as a function of Cd2+ concentration. Verapamil also decreased cadmium accumulation. Its effect compares well in magnitude with that which resulted from diamide treatment. No additive effect was observed when the cells were simultaneously treated with diamide and verapamil. The results suggest that a change in the GSH/GSSG ratio affects cadmium uptake. Further, calcium channels may be involved in cadmium uptake by A549-T27 cells in a fashion that is dependent on sulfhydryl status.

Azo Compounds↗
PubMed1987

Ion transport and cadmium-induced inhibition of ciliary activity and induction of swelling of epithelial cells in mouse trachea organ culture.

Swelling of epithelial cells and reduction of ciliary activity in mouse trachea organ culture occurred after incubation for 4 h with a rather low concentration of cadmium acetate (10 microM). Specific inhibitors of ion transport (Na+, K+, Cl-) such as furosemide, amiloride and ouabain did not mimic, abolish or increase the toxic effects induced by cadmium acetate. Exposure to cadmium acetate had no significant effect on electrolyte uptake (22Na+ and 86Rb+). These results suggest that the swelling of epithelial cells induced by cadmium acetate is not due to an osmotic swelling from an accumulation of electrolytes. Ba2+, known to have several biological properties in common with Ca2+, and to influence basolateral K+ flux, counteracted the toxic effects of cadmium acetate, whereas a more rapid and extensive swelling occurred with cadmium acetate in a medium without Ca2+. No effect on the uptake of 109Cd2+ was found with barium chloride, whereas in a medium without Ca2+ the Cd2+ uptake increased by 47%. Trifluoperazine (100 microM), a drug which in vitro binds tightly to calmodulin, imitated the toxic effects of 10 microM cadmium acetate. The combination of 10 microM cadmium acetate and 100 microM trifluoperazine resulted in an additive toxic effect. A possible mechanism for the cadmium acetate-induced swelling and inhibition of ciliary activity could, thus, be a disturbance of the regulatory activity of calmodulin.

Acetates↗
PubMed2006

Cadmium is acutely toxic for murine hepatocytes: effects on intracellular free Ca(2+) homeostasis.

We studied cadmium toxicity in murine hepatocytes in vitro. Cadmium effects on intracellular free Ca(2+) concentration ([Ca(2+)](i)) were assayed, using a laser scanning confocal microscope with a fluorescent probe, Fluo-3/AM. The results showed that administration of cadmium chloride (CdCl(2), 5, 10, 25 microM) resulted in a dose-dependent decrease of hepatocyte viability and an elevated aspartate aminotransferase (AST) activity in the culture medium (p<0.05 for 25 microM CdCl(2) vs. control). Significant increases of lactate dehydrogenase (LDH) activities in 10 and 25 microM CdC1(2)-exposed groups were observed (p<0.05 and p<0.01, respectively). A greatly decreased albumin content and a more malondialdehyde (MDA) formation also occurred after CdC1(2) treatment. The Ca(2+) concentrations in the culture medium of CdCl(2)-exposed hepatocytes were significantly decreased, while [Ca(2+)](i) appeared to be significantly elevated (p<0.05 or p<0.01 vs. control). We found that in Ca(2+)-containing hydroxyethyl piperazine ethanesulfonic acid-buffered salt solution (HBSS) only, CdCl(2) elicited [Ca(2+)](i) increases, which comprised an initially slow ascent and a strong elevated phase. However, in Ca(2+)-containing HBSS with addition of 2-aminoethoxydiphenyl borane (2-APB), CdCl(2) caused a mild [Ca(2+)](i) elevation in the absence of an initial rise phase. Removal of extracellular Ca(2+) showed that CdCl(2) induced an initially slow [Ca(2+)](i) rise alone without being followed by a markedly elevated phase, but in a Ca(2+)-free HBSS with addition of 2-APB, CdCl(2) failed to elicit the [Ca(2+)](i) elevation. These results suggest that abnormal Ca(2+) homeostasis due to cadmium may be an important mechanism of the development of the toxic effect in murine hepatocytes. [Ca(2+)](i) elevation in acutely cadmium-exposed hepatocytes is closely related to the extracellular Ca(2+) entry and an excessive release of Ca(2+) from intracellular stores.

Albumins↗
PubMed2004

Inside or outside a ligand cleft? Synthetic, structural, and kinetic inertness studies of zinc, cadmium, and mercury complexes of cross-bridged cyclam and cyclen.

Ethylene cross-bridging of the popular tetraazamacrocyclic ligand cyclam has led to metal complexes with enhanced kinetic inertness. The synthesis and spectral characterization of zinc(II), cadmium(II), and mercury(II) complexes of cross-bridged cyclam (L1) as well as cross-bridged cyclen (L2) are reported along with the details of our synthetic route to L2. X-ray structural studies revealed that all Zn(II) and Cd(II) cations are fully kappa(4)N-coordinated inside the respective ligand's molecular cleft with L1 providing the better fit for Zn(II). While Hg(II) is similarly coordinated to L2, it has been found to complex L1 outside the ligand cleft in a novel exo-kappa(2)N-mode. Solution NMR data of the kappa(4)N complexes are consistent with the presence of only a single cis-folded isomer in each case. Ligand (1)H and (13)C coupling to both (111,113)Cd and (199)Hg in their complexes can be clearly discerned. The relative kinetic inertness of representative cross-bridged complexes in acidic aqueous solution has been assessed and found to be in the following order: Zn(II) > Cd(II)[dbl greater-than] Hg(II). The data also reaffirm that cross-bridged cyclam ligand L1 forms a substantially more inert complex with zinc(II) than either the smaller cyclen analogue L2 or the unbridged 1,4,8,11-tetramethyl-cyclam L3.

Bridged-Ring Compounds↗
PubMed2006

Preconcentration system for cadmium and lead determination in environmental samples using polyurethane foam/Me-BTANC.

In this work, polyurethane foam (PUF) loaded with 2-(6'-methyl-2'-benzothiazolylazo)chromotropic acid (Me-BTANC) was packed in a minicolumn and it was used in an on-line preconcentration system for cadmium and lead determination. Optimum hydrodynamic and chemical conditions for metal sorption were investigated. The effects of several foreign substances on the adsorption of cadmium and lead were also reported. The enrichment factor obtained was 37 (Cd and Pb) for 180 s preconcentration time. The proposed procedures allowed the determination of metals with detection limits (3 sigma) of 0.80 and 3.75 microg L(-1) (0.10 and 0.47 microg g(-1) of solid sample) for cadmium and lead, respectively. The precision of the procedures was also calculated: 3.1 (Cd 10 microg L(-1)) and 4.4% (Pb 100 microg L(-1)). The accuracy of the procedure was checked by analysis of the certified reference materials Spinach Leaves and Fish Tissue. Cadmium and lead contents in environmental samples (black tea, spinach leaves, natural and tap water) were determined by applying the proposed procedure.

Animals↗
PubMed2005

The nitric oxide prodrug, V-PYRRO/NO, protects against cadmium toxicity and apoptosis at the cellular level.

The liver is an important target tissue of cadmium. The compound O2-vinyl 1-(pyrrolidin-1-yl)diazen-1-ium-1,2 diolate (V-PYRRO/NO) is a liver-selective nitric oxide (NO) prodrug that is metabolized by hepatic P450 enzymes to release NO in hepatocytes. In vivo, V-PYRRO/NO can protect against the toxicity of various hepatotoxicants, including cadmium. Since NO is an effective vasodilator, whether this protective effect against cadmium toxicity is at the level of the hepatic vascular system or actually within the liver cells has not been defined. Thus, we studied the effects of V-PYRRO/NO pretreatment on cadmium-induced toxicity and apoptosis in cultured rat liver epithelial (TRL 1215) cells. Cells were pretreated with V-PYRRO/NO at 500 or 1000 microM for up to 24 h, then exposed to cadmium (as CdCl2) for additional 24 h and cytotoxicity was measured. Cadmium was significantly less cytotoxic in V-PYRRO/NO (1000 microM) pretreated cells (LC50=6.1+/-0.6 microM) compared to control cells (LC50=3.5+/-0.4 microM). TRL 1215 cells acted upon the prodrug to release NO, producing nitrite levels in the extracellular media after 24 h of exposure to 500 or 1000 microM V-PYRRO/NO measured at 87.0+/-4.2 and 324+/-14.8 microM, respectively, compared to basal levels of 7.70+/-0.46 microM. V-PYRRO/NO alone produced small increases in metallothionein (MT), a metal-binding protein associated with cadmium tolerance. However, V-PYRRO/NO pretreatment greatly enhanced cadmium induction of MT. V-PYRRO/NO pretreatment also markedly reduced apoptotic cell death induced by cadmium (5 microM), apparently by blocking cadmium-induced activation of the c-Jun N-terminal kinase (JNK) pathway. Thus, the prodrug, V-PYRRO/NO, protects against the adverse effects of cadmium directly within rat liver cells apparently through generation of NO and, at least in part, by facilitation of cadmium-induced MT synthesis.

Animals↗
PubMed1975

Studies on the dominant-lethal and fertility effects of the heavy metal compounds methylmercuric hydroxide, mercuric chloride, and cadmium chloride in male and female mice.

Dominant-lethal effects of 10 mg/kg methylmercuric hydroxide were studied in male mice from two hybrid stocks and in females from one of these stocks. Two other compounds, mercuric chloride (2 mg/kg) and cadmium chloride (2 mg/kh), were studied only in females for dominant-lethal (in one hybrid stock) and reproductive capacity effects (in two hybrid and one mixed stocks). All compounds were administered in a single intraperitoneal injection. When males of one of the two stocks studied were treated with methylmercuric hydroxide, the females to which they were mated exhibited a slight reduction in the total number of implantations and in the number of living embryos. These reductions were accompanied by a very small increase in the incidence of dead implantations. In females, cadmium chloride had no detectable dominant-lethal or other fertility effects, except superovulation. On the other hand, the two mercury compounds slightly reduced the numbers of implants and living embryos in females subjected to dominant-lethal studies. The two mercury compounds also induced a slight reduction in that long-term reproductive performance of one stock of females. These results and those reported earlier by others, indicate that the mercury compounds studied so far are not potent inducers of dominant-lethal mutations in male and female mice. It is not clear whether the small effects on male or female fertility induced in some cases, particularly the increase in dead implantations and reductions in the number of living embryos, were attributable to dominant-lethal mutations or to nongenetic causes.

Animals↗
PubMed1993

Immunotoxic and hematotoxic effects of occupational exposures.

The toxic effects of environmental factors at work places on the hematopoietic and immune systems are of basic importance due to the time of exposure, lasting on average 8 hours daily during one week. Porphyrinurias and porphyrias have been observed after exposure to hexachlorobenzene, chlorinated dibenzodioxins, polychlorinated biphenyls, polybrominated biphenyls, vinyl chloride and lead. Aplastic anemia may occur after exposure to benzene, pesticides, arsenic, cadmium and copper compounds. Megaloblastic anemia has been noted in subjects exposed to arsenic, chlordane, benzene and nitrous oxide. Methemoglobinemia is induced by aromatic nitro and amino compounds. Hemolytic reactions caused by arsenic, methyl chloride, naphthalene, lead, cadmium and mercury compounds represent a separate problem. Immunodeficiencies resulting in decreased antitumor and antiinfectious immunity have been reported in subjects exposed to asbestos, ozone, dimethylsulphoxide, vinilidene chloride, and benzene homologues. Lymphocytopenia may be induced by manganese, lead, toluene and industrial noise. Neutropenia was marked after exposure to carbon disulphide, arsenic compounds, benzene and electromagnetic fields. Only a few reports concern the lymphocyte T3, T4 and T8 subpopulations. Electromagnetic fields (microwaves) cause an imbalance of that subpopulation, consisting of a decrease in the T8 cell count. The neutrophil enzymes, such as myeloperoxidase and alkaline phosphatase, decrease in their activity after exposure to polychlorinated biphenyls, carbon disulphide, chlorobenzene and DDT. A majority of agents cited include genotoxic effects reflected in chromosome aberrations and increased sister chromatid exchange and abnormal unscheduled DNA synthesis. Leukemia or lymphoma risk is increased after exposure to pesticides, electromagnetic fields, benzene and irradiation.

Chronic Disease↗
PubMed2004

Ultra-stable nanoparticles of CdSe revealed from mass spectrometry.

Nanoparticles under a few nanometres in size have structures and material functions that differ from the bulk because of their distinct geometrical shapes and strong quantum confinement. These qualities could lead to unique device applications. Our mass spectral analysis of CdSe nanoparticles reveals that (CdSe)(33) and (CdSe)(34) are extremely stable: with a simple solution method, they grow in preference to any other chemical compositions to produce macroscopic quantities. First-principles calculations predict that these are puckered (CdSe)(28)-cages, with four- and six-membered rings based on the highly symmetric octahedral analogues of fullerenes, accommodating either (CdSe)(5) or (CdSe)(6) inside to form a three-dimensional network with essentially heteropolar sp(3)-bonding. This is in accordance with our X-ray and optical analyses. We have found similar mass spectra and atomic structures in CdS, CdTe, ZnS and ZnSe, demonstrating that mass-specified and macroscopically produced nanoparticles, which have been practically limited so far to elemental carbon, can now be extended to a vast variety of compound systems.

Cadmium Compounds↗
PubMed1986

The staining properties of halo- and alkyl-thiazolylazophenol derivatives in histochemical staining of cadmium.

In the continuous research for a more sensitive chelator for cadmium, halothiazolylazodiethyaminophenol and alkylthiazolylazophenol derivatives were synthesized, and their staining sensitivity for cadmium chelates were examined with respect to a substituent group. 2-(4-Methyl- and 4,5-dimethyl-2-thiazolylazo)-5-diethylami-nonphenol showed low staining density in the 005-sections of cadmium, to date they showed the highest staining sensitivity for cadmium among the thiazolylazophenol analogs. The appropriate combination of substituent groups as based on their electron donative strength may be the decisive factor in determining the staining sensitivity of thiazolylazophenol analogs.

Animals↗
PubMed2006

[Study on solid phase extraction and spectrophotometric determination of cadmium with 2-[2-(5-bromoquinolinylazo)]-5-diethylaminophenol].

A new chromogenic reagent 2-[2-(5-bromoquinolinylazo)]-5-diethylaminophenol (5-Br-QADEAP) was synthesized, and its structure was verified by elemental analysis, infrared spectrum, and 1H nuclear magnetic resonance spectrum. The color reaction of 5-Br-QADEAP with cadmium was studied. In the presence of pH 8.0 buffer solution and Triton X-100 medium, 5-Br-QADEAP can react with cadmium(II) to form a stable 2 : 1 complex (5-Br-QADEAP: Cd(II). The molar absorptivity is 1.60 x 10(5) L x mol(-1) x cm(-1) at 595 nm. Beer's law is obeyed in the range of 0-1.0 microg x mL(-1). The cadmium ion in the samples can be enriched and separated by solid phase extraction with anion exchange resin cartridge. This method was applied to the determination of cadmium in water and food. The relative standard deviations are 2.5%-3.2%, and the recoveries are 96%-105%. The results are satisfactory.

Animals↗
PubMed2005

A novel thiocyanate-bridged dinuclear cadmium(II) complex: di-mu-thiocyanato-bis((methanol){4-nitro-2-[2-(dimethylamino)ethyliminomethyl]phenolato}cadmium(II)).

The title complex, [Cd2(C11H14N3O3)2(NCS)2(CH4O)2], is an interesting thiocyanate-bridged dinuclear cadmium(II) compound. It is located on a crystallographic inversion center. The CdII atom is six-coordinated in an octahedral configuration by one O and two N atoms of one Schiff base ligand and by the terminal N atom of a bridging thiocyanate ligand, defining the basal plane, and by the terminal S atom of another bridging thiocyanate ligand and by the O atom of a coordinated methanol molecule, occupying the axial positions. The molecules are linked through intermolecular O-HO hydrogen bonds, forming chains running along the b axis.

Cadmium↗
PubMed1990

Transport of organic compounds in renal plasma membrane vesicles of cadmium intoxicated rats.

Effects of cadmium intoxication on renal transport systems for various organic compounds were studied. Subcutaneous injections of CdCl2 (2 mg Cd/kg.day) for two to three weeks induced marked polyuria, glycosuria, and proteinuria without altering glomerular filtration rate. In renal cortical brush border membrane vesicles (BBMV) isolated from cadmium treated rats, Na(+)-dependent D-glucose uptake was markedly attenuated, and this was due to reduction in Vmax and not Km. Likewise, Na(+)-driven L-glutamate transport and H(+)-driven tetraethylammonium transport were significantly reduced. In renal cortical basolateral membrane vesicles (BLMV) of cadmium intoxicated rats, Na(+)-dependent succinate transport was drastically reduced. These results indicate that cadmium intoxication impairs various transport systems for organic compounds in the brush border and basolateral membranes of proximal renal tubules.

Cadmium Poisoning↗