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Synthesis of stable luminescent microspheres by a simple method.

An easy procedure for preparing microspheres containing CdSe/CdS core-shell quantum dots (QDs) was demonstrated. The luminescent properties of this microsphere were characterized by fluorescence microscopy and fluorescence spectrophotometry. Scanning electron microscopy was also used in this study. Laser confocal microscopy was carried out to describe the distribution of QDs in the microsphere. Especially, the stability of microspheres was investigated. It was found that the getting microsphere was very stable in water and showed values for physiological conditions. The inherent stability of the spheres, as well as their photostability, allows them to be used in biological applications.

Cadmium Compounds↗

Capability of coupled CdSe/TiO(2) for photocatalytic degradation of 4-chlorophenol.

The photocatalytic process using TiO(2) and coupled semiconductor in the photodegradation reaction of 4-chlorophenol (4-CP) was investigated. Nanosized titanium dioxide powder was synthesized via the sol-gel procedure and modified via the coupled photocatalysts. The microstructural and chemical properties of TiO(2) and coupled CdSe/TiO(2) were also examined. For CdSe/TiO(2) samples, the specific surface area was 7.0 m(2)/g and the deposition proportion of CdSe was approximately 27.6%. In the photocatalysis results, higher photodegradation efficiency of 4-CP was observed at higher pH values. In the UV 254 nm system, the degradation efficiency of 4-CP and TOC with sol-gel produced TiO(2) (TiO(2)(SG)) powder was higher than with commercial TiO(2)(RdH) powder. For the coupled semiconductor system (CdSe/TiO(2)), the apparent first-order rate constants were 1.35 x 10(-2), 4.33 x 10(-2), 2.0 x 10(-3) and 1.9 x 10(-3)min(-1) at the conditions of pH 7 (254 nm), pH 11 (254nm), pH 7 (365 nm), and pH 11 (365 nm). The disappearance of 4-CP under CdSe/TiO(2)(RdH) photoreaction at pH 7 and 365 nm condition is better than that of TiO(2)(RdH) system, with 30% versus 22% 4-CP reduction in 180 min. In the same condition, CdSe/TiO(2)(RdH) provided more photomineralization efficiency than that of TiO(2)(RdH) in terms of TOC reduction. Both 4-CP and TOC reduction were significant for systems illuminated at 254 nm. Considering the direct photolysis effect at 254 nm where 4-CP reduction is near 100% and TOC removal is nil, CdSe/TiO(2)(RdH) exhibits a 50% photomineralization efficiency and a nearly four times faster reaction rate than the single TiO(2)(RdH) semiconductor.

Cadmium Compounds↗

Cadmium-induced changes in the membrane of human erythrocytes and molecular models.

The structural effects of cadmium on cell membranes were studied through the interaction of Cd(2+) ions with human erythrocytes and their isolated unsealed membranes (IUM). Studies were carried out by scanning electron microscopy and fluorescence spectroscopy, respectively. Cd(2+) induced shape changes in erythrocytes, which took the form of echinocytes. According to the bilayer couple hypothesis, this result meant that Cd(2+) ions located in the outer monolayer of the erythrocyte membrane. Fluorescence spectroscopy measurements in IUM indicated a disordering effect at both the polar headgroup and the acyl chain packing arrangements of the membrane phospholipid bilayer. Cd(2+) ions also interacted with molecular models of the erythrocyte membrane consisting in bilayers of dimyristoylphosphatidylcholine (DMPC) and dimyristoylphosphatidylethanolamine (DMPE), representing classes of phospholipids located in the outer and inner monolayers the erythrocyte membrane, respectively. X-ray diffraction indicated that Cd(2+) ions induced structural perturbation of the polar headgroup and of the hydrophobic acyl regions of DMPC, while the effects of cadmium on DMPE bilayers were much milder. This conclusion is supported by fluorescence spectroscopy measurements on DMPC large unilamellar vesicles (LUV). All these findings point to the important role of phospholipid bilayers in the interaction of cadmium on cell membranes.

Cadmium Compounds↗

Characterization and crystal structure of cadmium(II) halide complexes with amino acids and their derivatives: VII. Crystal structures of aquadibromo(3-aminopropanoic acid)cadmium(II), dichloro(4-aminobutanoic acid)cadmium(II), diaquabis(aminohexanoic acid)cadmium(II) tetrachlorocadmium(II), and dibromo(azetidine-3-carboxylic acid)cadmium(II).

Seven cadmium complexes: [CdX2(Hapro)(H2O)n] (X: Cl(1), Br(2)), [CdX2(Hgaba)] (X: Cl(3), Br(4)), [Cd(Hahex)2(H2O)2][CdCl4] (5), and [CdX2(Haze-3)](H2O)n (X: Cl(6), Br(7)) have been prepared and investigated by means of IR and FT Raman spectra. The crystal and molecular structures of 2, 3, 5 and 7 were determined by a single-crystal X-ray diffraction method. In complex 2, the cadmium atom is in a distorted octahedral geometry, ligated by two carboxyl oxygen atoms of Hapro, a water molecule, and three bromine atoms; one is terminal and each of the other two is bridging two cadmium atoms to make a polymer. The structure of 3 consists of one-dimensional polymers bridged by two chlorine atoms and a carboxyl group. The carboxyl oxygen atoms of Hgaba coordinate forkedly to two cadmium atoms. The cadmium atom of [Cd(Hahex)2(H2O)2]2+ in complex 5 is in a distorted octahedral geometry, ligated by four carboxyl oxygen atoms of two molecules of Hahex and by two water molecules. [Cd(Hahex)2(H2O)2]2+ exists between two layers which are formed of infinite [CdCl4]2- chains. The carboxyl oxygen atoms of Hahex coordinate to the same cadmium atom. In complex 7, the cadmium atom is ligated by two carboxyl oxygen atoms and four bridging bromine atoms to make a polymer.

Amino Acids↗

Enhancement of the photoluminescence of CdSe quantum dots during long-term UV-irradiation: privilege or fault in life science research?

The present study describes an impressive enhancement of the photoluminescence (PL) intensity of low-temperature synthesized CdSe nanocrystals (75 degrees C) during long-term UV-irradiation. The integrated PL-intensity of CdSe core and CdSe/ZnS core/shell nanocrystals, dispersed in chloroform, enhanced about 3 and 6 times, respectively, during 9 h exposure to UV-light, without any significant changes in the characteristic absorbance spectra and shifting of PL-spectra. After termination of the irradiation a comparatively slow photobleaching was detected with tau(1/2) = 6 h for CdSe core and tau(1/2) = 14 h for CdSe/ZnS core/shell nanocrystals. The most impressive was the effect of UV-irradiation on the photoluminescence of water-soluble CdSe nanocrystals. The integrated PL-intensity enhanced about 10 times during 11 h exposure to UV-light and the improved PL-intensity was preserved during 3 days after termination of the irradiation without any significant photobleaching. The results are discussed in the context of application of CdSe nanocrystals as novel fluorophores in life science experiments.

Biological Science Disciplines↗

Synthesis of CdS nanoparticles in colloidal state and its possible interaction with tyrosine.

The basic objective is to develop a simpler method of preparation of the colloidal CdS nanoparticles with greater stability and to study interaction with tyrosine molecules. Average size of the particles in the colloid is found to be about 3 nm as probed by transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements. Effect of both sulfide enriched CdS as well as Cd(2+) enriched CdS on tyrosine is investigated both through absorbance and emission spectroscopy. Quenching of tyrosine emission followed Stern-Volmer relation and was found to be independent of temperature, indicating possible static quenching. However, Forster transfer between tyrosine and CdS can be suspected to mimic static quenching in addition to the charge transfer complexes. In the presence of Cd(2+) enriched CdS nanoparticles, the emission of tyrosine in phosphate buffer shows typical spectral broadening and a long wavelength increase in fluorescence emission. This may be attributed to the sensitized emission of CdS itself.

Cadmium Compounds↗

Effects of cadmium and copper on peroxidase, NADH oxidase and IAA oxidase activities in cell wall, soluble and microsomal membrane fractions of pea roots.

Twelve-day-old seedlings of pea (Pisum sativum L.) that were treated for 4 days by 20 and 100 micromol/l Cd(NO3)2 or CuSO4 showed a growth reduction in all organs. From root protein extracts, the activities of guaiacol peroxidase (GPX; EC 1.11.1.7), ascorbate peroxidase (APX; EC 1.11.1.11), coniferyl alcohol peroxidase (CAPX), NADH oxidase, and indole-3-acetic acid (IAA) oxidase were measured in covalently--and ionically--[symbol: see text] bound cell wall, soluble, and microsomal membrane fractions. With the exception of 20 micromol/l Cu, metal treatments enhanced GPX activity in all fractions. Only IAA oxidase activity was metal-elevated in the covalently bound cell wall fraction, while the ionic one showed Cd stimulation for all assayed enzymic activities. These effects were not entirely observed in Cu-treated plants, since APX and IAA oxidase activities were only enhanced in this fraction. However, soluble extract showed stimulation of APX activity, while in the microsomal fraction metal exposure also increased the activities of CAPX and NADH oxidase. Differential responses of root cell fractions to the presence of cadmium and copper ions are discussed in regard to the contribution of their enzymic capacities in antioxidant, lignification, and auxin degradation pathways. Comparisons between metals and dose effects are also underlined.

Cadmium Compounds↗

Growth parameters and photosynthetic pigments in leaf segments of Zea mays exposed to cadmium, as related to protection mechanisms.

The influence of cadmium on growth parameters and photosynthetic pigment content was studied in maize leaf segments differing in tissue maturity. Experiments were carried out with maize seedlings Zea mays L. cv. Hidosil treated with 25, 50, 100, 150 and 200 microM Cd for 14 days under low light conditions. Tissue age-dependent decrease of fresh mass, dry mass and area of the leaf segments was correlated with Cd concentration in the growth medium. Cd induced changes in chlorophyll and carotenoid contents, and the specific areas and densities of the leaf segments were dependent on age and metal concentration. Results are discussed with respect to the protection mechanisms in the leaf segments.

Cadmium Compounds↗

Heavy-metal-induced ethylene production in Arabidopsis thaliana.

Different plant parts varied in copper sulfate (CuSO(4)) and cadmium sulfate (CdSO(4))-induced ethylene production, inflorescences showed the greatest induction, while all other plant parts tested produced significantly less. Leaf age had a dramatic effect on CuSO(4) and CdSO(4)-induced ethylene production with the youngest leaves showing the greatest stimulation and as the age of the leaf increased there was a reduction in their ability to produce ethylene. However, there was no significant difference in CuSO(4), CdSO(4) and wound-induced ethylene production when whole rosettes were taken from plants that were 7, 14 or 21-day-old. The highest amount of CuSO(4) and CdSO(4)-induced ethylene production was produced in the root tip with regions below this producing less. CuSO(4) and CdSO(4)-induced ethylene production was also greatest from the tip of the inflorescence to 2cm below the tip and from this point down there was a reduction in ethylene production. When inflorescence stalks or leaves were treated with CuSO(4) or CdSO(4) over a range of concentrations from 0 to 800microM, there was an increase in ethylene production starting at 50microM with increasingly greater responses up to 400microM. There was no further increase at the 800microM CuSO(4) concentration; however, there was a slight decline with 800microM CdSO(4). Inflorescence stalks or leaves treated with either 400microM CuSO(4) or CdSO(4) exhibited a dramatic increase in ethylene production 2h following treatment initiation and remained high over a 24-h period with a decline in ethylene production after this time in inflorescence stalks but not the leaves. It was found that light caused a dramatic decrease in CuSO(4), CdSO(4) and wound-induced ethylene production in both inflorescence stalks and leaves. When inflorescence stalks or leaves were treated at 43 degrees C, there was a dramatic effect on CuSO(4), CdSO(4) and wound-induced ethylene production in each.

Arabidopsis↗

A comparative investigation of DNA strand breaks, sister chromatid exchanges and K-ras gene mutations induced by cadmium salts in cultured human cells.

Cadmium (Cd) is a toxic heavy metal of continuing occupational and environmental concern with a wide variety of adverse effects. Several studies have shown that cadmium produces DNA strand breaks, DNA-protein cross-links, oxidative DNA damage, chromosomal aberrations, dysregulation of gene expression resulting in enhanced proliferation, depressed apoptosis and/or altered DNA repair. This study was undertaken to investigate the ability of cadmium chloride (CdCl(2)) and cadmium sulphate (CdSO(4)) to induce point mutations in codon 12 of the K-ras protooncogene assessed by polymerase chain reaction-single strand conformation polymorphisms (PCR-SSCP) and RFLP-enriched PCR methods. Also their genotoxic effects were analyzed by the comet assay and sister chromatid exchanges test. The human lung fibroblast cell line MRC-5 was used for the experiments. Sister chromatid exchanges assay (SCEs) frequencies were significantly increased in cells exposed to cadmium salts in relation to controls (p<0.001). Despite the slow increment observed in the three comet parameters considered when cells were treated with cadmium chloride, significant differences between groups were only found in the variable comet moment (CM) (p<0.005). On the other hand, when cells were exposed to cadmium sulphate, the Kruskal-Wallis test showed highly significant differences between groups for migration, tail moment and comet moment parameters (p<0.001). Nevertheless, a null or weak point mutation induction in K-ras protooncogene was detected using polymerase chain reaction-low ionic strength-single strand conformation polymorphisms (PCR-LIS-SSCP) and RFLP-enriched PCR methods when cells were treated with cadmium salts. Thus, inorganic cadmium produces genotoxicity in human lung fibroblast MRC-5 cells, in the absence of significant point mutation of the K-ras gene.

Cadmium Chloride↗

Involvement of ethylene and lipid signalling in cadmium-induced programmed cell death in tomato suspension cells.

Cadmium-induced cell death was studied in suspension-cultured tomato (Lycopersicon esculentum Mill.) cells (line MsK8) treated with CdSO(4). Within 24 h, cadmium treatment induced cell death in a concentration-dependent manner. Cell cultures showed recovery after 2-3 days which indicates the existence of an adaptation mechanism. Cadmium-induced cell death was alleviated by the addition of sub muM concentrations of peptide inhibitors specific to human caspases indicating that cell death proceeds through a mechanism with similarities to animal programmed cell death (PCD, apoptosis). Cadmium-induced cell death was accompanied by an increased production of hydrogen peroxide (H(2)O(2)) and simultaneous addition of antioxidants greatly reduced cell death. Inhibitors of phospholipase C (PLC) and phospholipase D (PLD) signalling pathway intermediates reduced cadmium-induced cell death. Treatment with the G-protein activator mastoparan and a cell permeable analogue of the lipid signal second messenger phosphatidic acid (PA) induced cell death. Ethylene, while not inducing cell death when applied alone, stimulated cadmium-induced cell death. Application of the ethylene biosynthesis inhibitor aminoethoxy vinylglycine (AVG) reduced cadmium-induced cell death, and this effect was alleviated by simultaneous treatment with ethylene. Together the results show that cadmium induces PCD exhibiting apoptotic-like features. The cell death process requires increased H(2)O(2) production and activation of PLC, PLD and ethylene signalling pathways.

Apoptosis↗

Interactions of pigments and opacifiers on color stability of MDX4-4210/type A maxillofacial elastomers subjected to artificial aging.

STATEMENT OF PROBLEM: The color instability and degradation of maxillofacial elastomers limit the function and cosmetic quality of facial prostheses. PURPOSE: The purpose of this study was to measure the interactions of oil pigments plus dry earth opacifiers at 5%, 10%, and 15% by volume in stabilizing the color of MDX4-4210/type A silicone elastomers before and after artificial aging. MATERIAL AND METHODS: In the first part of the study, each of 5 opacifiers (Georgia kaolin powder neutral, kaolin powder calcined, Artskin white, dry pigment titanium (Ti) white, or Ti white artists' oil color) at 10% concentrations were combined with each of 5 oil pigment types (no pigment, cadmium-barium red deep, yellow ochre, burnt sienna, or a mixture of the 3 pigments), for a total of 25 experimental groups of elastomers. In the second part of the study, 50 experimental groups of elastomers were made by combining 1 of 5 opacifiers at 5% and 15% concentrations with 1 of 5 oil pigments as in Part 1. Five specimens of each elastomer were tested, for a total of 375 specimens. In each part of the study, all specimens were aged in an artificial aging chamber. CIE L*a*b* values were measured by a spectrophotometer. The color differences (DeltaE*) were subjected to repeated-measures analysis of variance. Mean values were compared by Tukey-Kramer intervals (alpha = .05). RESULTS: In Part 1, when the opacifiers were tested at 10% concentration, Ti white oil color had the most color change, and dry pigment Ti white had the least; all other opacifiers were not significantly different from each other. In Part 2, at 5%, Ti white oil color had the most color change; all other opacifiers were not significantly different from the others. At 15%, Ti white oil color again had the most color change, followed by Artskin white, kaolin powder calcined, and Georgia kaolin; Ti white dry earth pigment had the least color change. Overall, 5% Artskin white had less color change than the 15%, whereas 15% dry pigment Ti white had less color change than the 5% (P < .001). The 5% and 15% of other opacifiers were not significantly different. CONCLUSIONS: At all 3 concentrations, oil pigments mixed with opacifiers helped protect the MDX4-4210/type A silicone elastomer from color degradation over time. Dry pigment Ti white remained the most color stable over time, followed by the pigments mixed with kaolin powder calcined, Georgia kaolin, Artskin white, and Ti white artists' oil color.

Barium Sulfate↗

Cadmium-induced postaxial forelimb ectrodactyly: association with altered sonic hedgehog signaling.

Administration of CdSO(4) to C57BL/6 mice at day 9.5 of gestation induces a high incidence of postaxial forelimb ectrodactyly in the offspring. We propose that Cd(2+) exposure impairs the process of anterior/posterior formation in the limb bud, a process that is directed by Sonic hedgehog (Shh) signaling. We show that exposure of the mouse embryo to Cd(2+) disrupts Shh signaling as measured by polarizing activity of mouse limb bud ZPA grafted to a host chick wing, and activity of a Gli:luciferase reporter exposed to limb bud lysates. Yet the expression of Shh and its translation are not affected by Cd(2+) exposure. We propose that teratogen exposure affects the processing of Shh in the cells in which it is made.

Animals↗

Fourier-transform infrared and Raman spectra of cysteine dichloride cadmium(II) anion DFT: B3LYP/3-21G(d) structural and vibrational calculations.

The cysteine dichloride cadmium(II) potassium was synthesized and the structural analysis was carried out through the following methods: determination of the C, H, N, S and O contents, thermogravimetry, infrared and Raman spectra. Assuming Cd-S, Cd-O (O-carboxilate) and Cd-N bonds, several hypothetical structures were calculated by means DFT: B3LYP/3-21G(d) quantum mechanical method. The calculations shows that the Cd-S and Cd-N central bonds are favoured in the anion complex formation [Cd(Cys)Cl2]-, being the stabilization energy 55.52 kcal mol(-1) lower than isotopomers with Cd-S and Cd-O central bonds. Features of the infrared and Raman spectra confirm the theoretical structural prediction. Full assignment of the vibrational spectra is proposed based on the DFT procedure, and in order to confirm the C-H, N-H, C-C, C-N, Cd-N, Cd-S and Cd-Cl stretching and the HNH and HCH bending, a normal coordinate analysis based on local symmetry force field for -SC(H2)C-, -CdN(H2)C- and -SCd(Cl2)N- fragments was carried out.

Anions↗

The interaction between some diamines and CdSe quantum dots.

The interaction of some diamines (ethylenediamine (EDA), 1,6-hexanediamine (HDA), o-phenylenediamine (OPD)) with CdSe quantum dots (QDs) is reported. With increasing concentration of EDA from 0 to 2.0 x 10(-6) mol l(-1), slight fluorescence enhancement is observed. However, the CdSe QDs fluorescence quenching is seen at relatively higher concentration of EDA. There is a red-shift of 0-7 nm in fluorescence emission spectra of CdSe QDs when the concentration of EDA is changed from 2.0 x 10(-6) to 8.0 x 10(-6) mol l(-1). The resonance light scattering (RLS) spectra of CdSe QDs have little change when the concentration of EDA is less than 5.0 x 10(-6) mol l(-1). It indicates there are little large particles formed in the solution. However, a significant increase of the RLS is observed in the 300-500 nm wavelength range after adding higher concentration than 5.0 x 10(-6) mol l(-1) EDA, which could be attributed to the large particles formed. The interaction between HDA and CdSe QDs is similar to that of EDA. However, with the OPD, it is found that the interaction is much different from those of EDA, HDA, and that the quenching, even at low concentration, is effective for CdSe QDs emission. The quenching phenomenon could be explained by a surface bound complexation equilibrium model.

Cadmium Compounds↗

Theoretical studies of lattice distortions around the impurity ions in V2+ doped CdCl2, CdI2 and PbI2.

The lattice distortions around the impurity ions in V(2+) doped CdCl(2), CdI(2) and PbI(2) are theoretically studied from the perturbation formulas of the spin Hamiltonian (SH) parameters zero-field splitting, g factors and the hyperfine structure constants for a 3d(3) ion in trigonal symmetry based on the cluster approach. In these formulas, the contributions from the s-orbitals of the ligands are taken into account. Based on the studies, it is found that the local angles beta (between the impurity-ligand bonding lengths and the C(3) axis) in the impurity centers are smaller than the angles beta(H) in the hosts. The calculated SH parameters based on the above local angles beta show better agreement than those on neglecting of the ligand s-orbital contributions (and those on the host angles beta(H)) with the experimental data.

Cadmium Chloride↗

CdTe surface roughness by Raman spectroscopy using the 830 nm wavelength.

A Raman spectroscopic study was performed to detect the surface roughness of a cadmium telluride (CdTe) wafer sample, using the 514.5, 632.8 and 830.0 nm excitations wavelengths. To verify the relation between the roughness and the structure of Raman spectra, in certain zones of the sample, we measured their roughness with an atomic force microscopy. It was found that, using the 830 nm wavelength there is a direct correspondence between the spectrum structure and the surface roughness. For the others wavelengths it was found, however, that there is not a clearly correspondence between them. Our results suggest that, using the excitation wavelength of 830 nm the Raman spectroscopy can be used as an on-line roughness monitor on the CdTe growth.

Cadmium Compounds↗

Quantitative determination of proteins at nanogram levels by the resonance light-scattering technique with composite nanoparticles of CdS/PAA.

This paper describes the development of composite nanoparticles. A novel composite nanoparticle has been prepared by an in situ polymerization method. The nano-CdS has been prepared, then the polymerization of acrylic acid (AA) was carried out by initiator potassium persulfate (KPS) under ultrasonic irradiation. The surface of the composite nanoparticles was covered with abundant carboxylic groups (-COOH). The nanoparticles are water-soluble, stable and biocompatible. Reaction of the composite nanoparticles with proteins results in an enhanced resonance light scattering (RLS) at 380 nm. Based on this, a new resonance light-scattering (RLS) method was developed for the determination of proteins including BSA, HSA and human gamma-IgG. Under the optimum conditions, the enhanced RLS intensity is linearly proportional to the concentration of proteins. The liner range is 0.1-15 microgmL(-1) for HSA, 0.2-20 microgmL(-1) for BSA and 0.1-50.0 microgmL(-1) for human gamma-IgG, respectively. The method has been applied to the determination of the total protein in human serum samples collected from the hospital and the results are in good agreement with those reported by the hospital. This method proved to be very sensitive, rapid, simple and tolerant of most interfering substances.

Animals↗