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ESCA study on dental alloy surfaces modified by Ga-Sn alloy.

A new, simple surface modification method for adherend metals has been developed. It gives high bond strength and superior water durability to dental precious-metal alloys bonded with 4-META/MMA-TBB resin. However, there was no effect on the bonding of Ag-In-Zn alloy and base-metal alloys. In the present study, the alloy surfaces modified by the new method were analyzed by ESCA and SEM for determination of details of the modification effect. A new alloying layer containing Ga and Sn was formed on the precious-metal alloys. The main factor for excellent adhesion to be achieved was the formation of a very thin layer of Ga2O3 and SnO2, less than 1-2nm thick, on the alloy surface. A thicker modified layer, as formed on the Ag-In-Zn and Ni-Cr alloys, led to low bonding ability.

Acrylic Resins↗

Induction of chromosome changes by metal compounds in cultured CHO cells.

The effect of 4 metal salts on the induction of chromosome aberrations and sister chromatid exchange (SCE) in cultured Chinese hamster ovary (CHO) cells was investigated. It was observed that CdCl2, NiCl2, CrO3 and HgCl2 were effective in causing various types of chromosome aberrations. The percentages of abnormalities increased with increasing doses of the metals used. These metal compounds also raised the SCE rates compared to 5-bromo-2'-deoxyuridine controls. The importance of rapid screening of potentially hazardous metals is described.

Animals↗

Quest for the molecular mechanism of chromium action and its relationship to diabetes.

Despite forty years of research on the potential role of chromium in carbohydrate and lipid metabolism, significant progress has only recently been made regarding the mode of action of chromium at a molecular level. The oligopeptide low-molecular-weight chromium-binding substance (LMWCr) may function as part of a novel insulin-signaling autoamplification mechanism. The proposed mechanism of action also sheds some light on the potential of chromium-containing compounds as nutritional supplements or in the treatment of adult-onset diabetes and other conditions. The potential relationship between the results of recent studies on diabetic patients and the proposed mode of action of LMWCr are discussed.

Chromium↗

Oxide compounds on Ni-Cr alloys.

Five Ni-Cr alloys were studied in order to identify the compounds formed on the alloy surface during oxidation under conditions similar to those encountered during dental laboratory procedures prior to application of porcelain. After the alloys were oxidized, the films covering the surfaces were removed with the aid of a Br-methanol solution. X-ray diffraction was used to analyze the compounds formed. Oxides of nearly all elements contained by the alloys were found after low-temperature (650 degrees C) oxidation, while NiO and particularly Cr2O3 were predominant after oxidation at high temperatures (1000 degrees C).

Aluminum Oxide↗

Mechanisms of toxicity/carcinogenicity and Superfund decisions.

Heavy metals that contaminate soils and water usually exist in various oxidation states and form a number of compounds with different physical and chemical characteristics. These differences are often reflected in dramatic variation in toxicokinetic and biologic properties. Such variation in properties, critical in determining intrinsic toxicity, often causes a great deal of uncertainty in analyses of public health risks at sites where metal exposure is evaluated. In the Superfund program, such uncertainties may substantially undermine attempts to characterize potential impacts to populations exposed to metals from improperly disposed waste. In the case of chromium, risk assessment uncertainties can be considerable and fall generally into two categories. First, there is almost no information on potential health effects due to chronic oral exposure to chromium-containing compounds, and a nonquantifiable and probably large uncertainty exists in establishing no-effect levels. In fact, reference doses (RfDs) for CrIII and CrVI are based on chronic studies in which no adverse effects were seen even at the highest dose. Considerations of bioavailability, deduced from site characterization data, and acute toxicity indicate that general application of these RfDs may lead to highly inaccurate estimations of risk. Second, because of the ready reduction of CrVI in biological systems, it has not been possible to separate effects of CrVI from those of CrIII. Thus, data on the relative toxicity and carcinogenicity of these two species is sparse and difficult to interpret. Moreover, kinetic considerations make it difficult to determine the site and rates of reduction of CrVI. This makes prediction of target site concentrations of the two species difficult.(ABSTRACT TRUNCATED AT 250 WORDS)

Administration, Oral↗

The relationship between monomer composition and physical properties of light-cured opaque resin.

Light-cured opaque resins were prepared using four types of monomer liquids and titanium dioxide powder. This study investigated the relationship between the monomer composition and the physical properties of light-cured opaque resin. Depth of cure, KHN, residual monomer eluent, and bond strength between the opaque resin and cobalt-chromium alloy were measured. The physical properties of triethyleneglycol dimethacrylate (TEGDMA)-based compositions were superior to those of methyl methacrylate (MMA)-based compositions. Viscosity of the opaque resin's liquid monomer was enhanced by 1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimeth ylhexane (UDMA). The TEGDMA-based light-cured opaque resins showed excellent physical properties and may be clinically acceptable in bonding prosthodontic composite to metal frameworks.

Acrylic Resins↗

Sorption of phosphate and Cr(VI) by Fe(III) and Cr(III) hydroxides.

Understanding the chemical behavior and interactions of Cr(VI) ( e.g., HCrO(4)(-)) and other anions, such as orthophosphate (P) with insoluble metal hydroxides ( i.e., Cr[III] and Fe[III]) in disposal landfills or in chromite ore processing residue (CORP)-enriched soil is very important in predicting the movement and the fate of Cr(VI). This study evaluates the sorption behavior of P and Cr(VI) by Fe(III) ( i.e., ferrihydrite), Cr(III) ( i.e., Cr[OH](3)), and coprecipitated Fe(III)/Cr(III) hydroxides. These metal hydroxide sorbents were synthesized, and sorption of P and Cr(VI) were conducted at different pH using a batch technology. Our results show that P and Cr(VI) sorption by metal hydroxides decreased with increasing suspension pH. Greater decrease in P sorption was observed when Cr(III) was present in the structures of hydroxides. Following the sorption of low concentration of P ( i.e., 0.5 mM), the sorption of subsequently added Cr(VI) by hydroxides was less influenced. However, Cr(VI) sorption was greatly inhibited when high concentration of P ( i.e., 10 mM) prereacted with hydroxides, particularly in Fe(III) hydroxide system. Results also indicated that high concentration of Cr(VI) (10 mM) could dissolve Cr(III) hydroxide at pH 3 and reprecipitate as an amorphous form of Cr(VI) and Cr(III) compound at pH about 6.5. Although coprecipitation of Cr(VI) with Cr(III) can inhibit Cr(VI) movement through soil profiles, the inhibition seems to be low due to the gradual release of Cr(VI) with increasing pH.

Adsorption↗

Effects of steric constraint on chromium(III) complexes of tetraazamacrocycles, 2. Comparison of the chemistry and photobehavior of the trans-dichloro- and trans-dicyano- complexes of cyclam, 1,4-C2-cyclam, and 1,11-C3-cyclam.

The synthesis and characterization of several Cr(III) complexes of the constrained macrocyclic ligand 1,11-C3-cyclam (1,4,8,11-tetraazabicyclo[9.3.3]heptadecane) is reported. Only trans complexes are formed, and the structure of trans-[Cr(1,11-C3-cyclam)Cl2]PF6 is presented. The chemical and photophysical behavior of the 1,11-C3-cyclam complexes are compared with those of the corresponding cyclam (1,4,8,11 tetraazacyclotetradecane) and 1,4-C2-cyclam (1,4,8,11-tetraazabicyclo[10.2.2]hexadecane) complexes. The aquation rate of trans-[Cr(1,11-C3-cyclam)Cl2]+ is similar to that of the corresponding 1,4-C2-cyclam complex and is more than 5 orders of magnitude faster than the cyclam counterpart. A monotonic increase in the extinction coefficient is observed on going from the cyclam complexes to the 1,11-C3-cyclam complexes to the 1,4-C2-cyclam complexes, and this is related to the degree of centrosymmetry in each complex. The trans-[Cr(1,11-C3-cyclam)(CN)2]+ complex is a weak emitter in aqueous solution with a room-temperature emission maximum at 724 nm (tau=23 micros). Like the corresponding 1,4-C2-cyclam complex (tau=0.24 micros), the 1,11-C3-cyclam complex shows no deuterium-isotope effect in room-temperature solution. This is in marked contrast to the corresponding cyclam complex which has an emission lifetime of 335 micros and a significant deuterium isotope effect in room-temperature solution. Low temperature (77K) data are also presented in an attempt to understand the differences in photophysical behavior.

Aza Compounds↗

Urinary excretion of brush-border antigen revealed by monoclonal antibody: early indicator of toxic nephropathy.

Mouse monoclonal antibodies against brush-border antigens of the proximal tubule of human kidney were produced by the hybridisation technique. The urinary excretion of a brush-border protein with an apparent molecular weight of 50 000 (BB-50) was measured by a sandwich enzyme-linked immunosorbent assay with a mouse IgG1 against BB-50 and a polyclonal rabbit antiserum against human kidney as coating and second antibodies. The urinary excretion of BB-50 was fifty times higher in patients treated with cisplatin than in a matched control group and twice as high in workers occupationally exposed to water-soluble chromium(VI) compounds as in their matched controls. These findings suggest that the urinary excretion of kidney antigens revealed by monoclonal antibodies is a very sensitive and specific test for the assessment of toxic nephropathies.

Adolescent↗

Quadruply Bonded Dichromium Complexes with Variously Fluorinated Formamidinate Ligands.

Complexes of chromium with various amidinate anions of N,N'-di(biphenyl)formamidine (DbiPhF), N,N'-di(pentafluorophenyl)formamidine (DPh(F)()5F), N,N'-di(p-fluorophenyl)formamidine (DPh(p)(-)(F)F), N,N'-di(o-fluorophenyl)formamidine (DPh(o)(-)(F)F), N,N'-di(3,5-fluorophenyl)formamidine (DPh(3,5)(-)(F)F), and N,N'-di(m-fluorophenyl)formamidine (DPh(m)(-)(F)F) have been synthesized and structurally characterized to study the response of the M-M multiple bond to the donor capacity of the ligand by varying the substituents of the aromatic rings. All six of these dinuclear fluorinated amidinate derivatives of the chromium(II) compounds have the paddlewheel configuration. The synthetic route involves the reaction of CrCl(2) with the corresponding lithium salt of the ligands, LiDArF (where Ar = o-C(6)H(4)F, m-C(6)H(4)F, p-C(6)H(4)F, p-C(6)H(4)C(6)H(5), C(6)F(5), or 3,5-C(6)H(3)F(2)). Compounds [Cr(2)(DPh(p)(-)(F)F)(4)] (1), [Cr(2)(DPh(m)(-)(F)F)(4)] (2), [Cr(2)(DPh(3,5)(-)(F)F)(4)].C(6)H(14) (3.C(6)H(14)), and [Cr(2)(DbiPhF)(4)].0.7CH(2)Cl(2) (4.0.7CH(2)Cl(2)) show no variation in the Cr-Cr quadruple bond length, even though the ligands have very different basicities. In the solid state, [Cr(2)(DPh(F)()5F)(4)] (5) shows close axial contacts between the o-F atoms and the chromium metal centers. The (19)F NMR show an unresolved and broad signal for all o-F atoms that cannot be resolved even at very low temperature. To assess the efficiency of the contacts, [Cr(2)(DPh(o)(-)(F)F)(4)] (6) was prepared.( )()The crystal structure shows the same kind of Cr.F interactions as in 5, and an elongation of the Cr-Cr quadruple bond, compared with the values for the complexes 1, 2, 3, and 4. These new complexes reveal that the electronic contribution of the ligand basicity to the M-M bond is smaller and less important than the axial interactions of the chromium centers. Crystal data: for 1, orthorhombic, space group Fddd with a = 25.25(7) Å, b = 26.752(12) Å, c = 28.57(4) Å, alpha = beta = gamma = 90 degrees, and Z = 16; for 2, triclinic, space group P&onemacr; with a = 9.606(12) Å, b = 9.727(10) Å, c = 13.249(11) Å, alpha = 69.24(1) degrees, beta = 73.84(2) degrees, gamma = 84.24(2) degrees, and Z = 1; for 3.C(6)H(14), triclinic, P&onemacr; with a = 10.8274(10) Å, b = 13.739(2) Å, c = 18.152(4) Å, alpha = 83.25(1) degrees, beta = 75.61(2) degrees, gamma = 70.246(10) degrees, and Z = 2; for 4.0.7CH(2)Cl(2), triclinic P1 with a = 9.689(2) Å, b = 13.7088(3) Å, c = 16.844(3) Å, alpha = 69.90(3) degrees, beta = 87.10(3) degrees, gamma = 70.13(3) degrees, and Z = 1; for 5, monoclinic, C2/c with a = 19.114(3) Å, b = 18.957(3) Å, c = 29.923(6) Å, beta = 97.27(1) degrees, and Z = 4; for 6, triclinic, P&onemacr; with a =10.225(2) Å, b = 11.312(2) Å, c = 11.797(3) Å, alpha = 117.08(1) degrees, beta = 96.432(2) degrees, gamma = 107.52(2) degrees, and Z = 1.

Journal Article↗

Centrosymmetric aliovalent KTP isomorphs KM(III)0.5Nb0.5OPO4 (M = Cr and Fe).

Aliovalent KTP isomorphic compounds potassium chromium niobium oxide phosphate, KCr0.5Nb0.5OPO4, and potassium iron niobium oxide phosphate, KFe0.5Nb0.5OPO4, exhibit structures that differ from that of the non-centrosymmetric KTiOPO4. There are two crystallographically independent octahedral sites, M1 and M2, statistically occupied by Nb and Cr (or Fe) atoms. The M1O6 and M2O6 octahedra are connected alternately to form a chain with a cis-trans arrangement. The Nb atoms prefer the M2 sites arranged in a cis-like configuration. Each PO4 tetrahedon has the P atom on a twofold axis. Site-splitting at the K-atom position is observed in both compounds. In the isomorphous structures, one Nb atom lies on an inversion centre and the other on a twofold axis. Similarly with the pairs of Fe/Cr sites, one is on an inversion centre and the other on a twofold axis.

Journal Article↗

Lime enhanced chromium removal in advanced integrated wastewater pond system.

The removal of trivalent chromium from a combined tannery effluent in horizontal settling tanks and subsequent Advanced Integrated Wastewater Pond System (AIWPS) reactors was investigated. The raw combined effluent from Modjo tannery had pH in the range of 11.2-12. At this pH, a trivalent chromium removal of 46-72% was obtained in the horizontal settling tanks after a one-day detention time. Trivalent chromium precipitated as chromium hydroxide, Cr(OH)3. 58-95% Cr(III) was removed in the advanced facultative pond (AFP) where the water column pH of 7.2-8.4 was close to pH 8, which is the optimum precipitation pH for trivalent chromium. Chromium removals in the secondary facultative pond (SFP) and maturation pond (MP) were 30-50% and 6-16%, respectively. With Cr(III) concentration of 0.2-0.8 mg/l in the final treated effluent, the AIWPS preceded by horizontal settling tanks produced effluent that could easily meet most of the current Cr(III) discharge limits to receive water bodies.

Calcium Compounds↗

Methodological aspects of assessing atmospheric contamination with metal aerosols in the vicinity of thermal power complexes.

A study of metal aerosols content in waste steam-containing gases from a thermal power station operating on oil fuel revealed that the concentrations of V2O5, Al2O3, Fe2O3, MnO2 and Cr2O3 are not influenced by the operational mode, type of boiler, the mean ratios being 1 : 0, 3 : 0, 27 : 0, 2 : 0, 03 : 0 and 0.25 respectively. Comparing the metal content in oil fuel and waste gases showed that no more than 10% of the studied compounds are sorbed on the boiler walls, the remaining 90% being released into the atmosphere. It is suggested that V2O5 be determined as an integral indicator with the aim of rapid hygienic assessment of the extent of atmospheric contamination with metal aerosols. The presented results may be used in preventive and regular sanitary surveillance during thermal power plant designing, construction and reconstruction.

Aerosols↗

Colorimetric diffusion-reflection imaging high-throughput analysis of organic or inorganic compounds.

A colorimetric diffusion-reflection imaging (CDRI) high-throughput analytical technology was developed for library analysis. In the investigation, quartz sands were employed as light diffusion-reflection media. Inorganic and organic compounds with characteristic absorption bands in visible light could be quantified by this method. In the current investigation, compounds such as CrCl3, KMnO4, methylene blue, and acrolein were employed as substrates, and the UV spectrometer and traditional GC (with thermal conductivity detector) were employed to check the reliability of our CDRI technology. The current technology is capable of analyzing more then 100 samples simultaneously. Relative errors below 10% were achieved.

Acrolein↗

Influence of reducing compounds on the formation of DNA-protein cross-links in HL-60 cells induced by hexavalent chromium.

The influence of reducing compounds on the formation of DNA--protein cross-links induced by hexavalent chromium was studied in the human cell line HL-60. Analysis of cytoplasmic concentration of ascorbic acid and glutathione by HPLC in these cells showed that ascorbic acid was not detectable (detection limit: 0.1 nmol). The cellular content of glutathione was low (6 nmol/million cells). It could easily be depleted with diethylmaleate. The effect of glutathione, ascorbic acid and ascorbyl palmitate alone, or glutathione in combination with ascorbyl palmitate was investigated. It could be shown that glutathione increased DNA--protein cross-links in HL-60 cells by chromate significantly in a dose dependent manner, while pre-incubation with L-ascorbic acid and L-ascorbic acid-6-hexadecanate (ascorbyl palmitate) did not change the cross-linking activity of chromate significantly. Ascorbyl palmitate counteracted the increasing effect of glutathione on the concentration of DNA--protein cross-links in HL-60 cells after exposure to chromate. As ascorbic acid reacts much faster with hexavalent chromium at physiological pH than glutathione does, this suggests an influence of the reaction velocity of the redox reaction between hexavalent chromium and the reducing compounds on the toxification of Cr(VI) and formation of DNA--protein cross-links.

Antimutagenic Agents↗

Bioaccumulation and toxicology of chromium: implications for wildlife.

The major source of exposure to Cr for wild birds and mammals is through ingestion with food. Chromium(VI) compounds are absorbed significantly more efficiently (2-10% of dose) from the GI tract than inorganic Cr(III) compounds (0.5-3%), due to the increased membrane permeability of the former. Transfer of Cr(VI) into mammalian fetuses has been documented at oral doses of 500 mg Cr/L in drinking water, and injected single doses of 5 mg Cr(VI)/kg BW in dams were teratogenic. Cr concentration data for mammalian and avian wildlife species and their potential food organisms are scarce. Worldwide, fewer than 50 species of free-living mammals and birds have been surveyed with regard to tissue Cr concentrations. Tissue concentrations in animals living in habitats remote from sources of Cr contamination range from approximately 0.1-15 micrograms/g DW depending on the species and tissue analyzed. In habitats experiencing Cr pollution, levels can be up to two orders of magnitude higher. Eisler (1986) suggested that tissue concentrations in wildlife > 4 micrograms/g DW be considered to indicate likely contamination by Cr. Bone tissue often accumulates higher concentrations than other tissues in animals chronically exposed to Cr. Measuring concentrations only in the liver and/or kidneys has been a common practice, yet these organs failed to show evidence of extant Cr contamination in some cases. It is recommended that analysis of the bone, liver, and kidneys be a minimum requirement for future Cr biomonitoring studies. Concentrations in fur or feathers can be extremely variable even among individuals within the same habitat. At best, concentrations in fur and feathers might be used to indicate relative levels of airborne Cr contamination. The toxicological significance of "elevated" Cr concentrations is largely unknown because toxicological data on free-living wildlife species are virtually nonexistent. Based on controlled dosing studies in which Cr compounds were administered orally to experimental animals, dietary Cr concentrations > or = 10 micrograms/g DW in food should be considered potentially harmful to the health and reproductive success of wildlife consumers. Certain species of fish and aquatic invertebrates are sensitive to Cr, showing reduced survival or growth at Cr(VI) concentrations > 10 micrograms/L. The elimination of these organisms from environments contaminated with Cr may have detrimental effects on wild birds and mammals that depend on such organisms for food.(ABSTRACT TRUNCATED AT 400 WORDS)

Animals↗

On the recovery of single spots with the flr phenotype in the wing spot test in Drosophila.

Graf et al. (U. Graf, F.E. Würgler, A.J. Katz, H. Frei, H. Juon, C.B. Hall, P.G. Kale, Somatic mutation and recombination test in Drosophila, Environment Mutagen. 6 (1984) 153-188.) described the overall results of assays of a series of compounds in the Drosophila wing spot test as indicating that single mwh spots appeared most frequently, followed by less frequent twin spots with both mwh and flr cells and lastly the 'quite rare' single flr spots. Data are presented below demonstrating that some compounds behave in a manner consistent with the above description, whereas others do not in that the frequency of single flr spots is equal to or exceeds that of twin spots and cannot be described as occurring 'rarely'. It is suggested that (large) flr singles be used as a measure of mutations/deletions directly from treated transheterozygotes. An argument is presented questioning the use of treated mwh +/+ TM3 individuals as an assay of mutations/deletions at the mwh+ locus.

Animals↗

Lung cancer in Yorkshire chrome platers, 1972-97.

OBJECTIVES: To investigate mortality from lung cancer in chrome platers, a group exposed to chromic acid. METHODS: The mortality of a cohort of 1087 chrome platers (920 men, 167 women) from 54 plants situated in the West Riding of Yorkshire, United Kingdom, was investigated for the period 1972-97. All subjects were employed as chrome platers for >/=3 months and all were alive on 31 May 1972. Mortality data were also available for a cohort of 1163 comparison workers with no known occupational exposure to chrome compounds (989 men, 174 women). Information on duration of chrome work and smoking habits collected for a cross sectional survey carried out in 1969-72 were available for 916 (84.3%) of the chrome platers; smoking habits were available for 1004 (86.3%) comparison workers. Two analytical approaches were used, indirect standardisation and Poisson regression. RESULTS: Based on serial mortality rates for the general population of England and Wales, significantly increased mortality from lung cancer was observed (obs) in male chrome platers (obs 60, expected (exp) 32.5, standardised mortality ratio (SMR) 185, p<0. 001) but not in male comparison workers (obs 47, exp 36.9, SMR 127). Positive trends were not shown for duration of employment exposed to chrome, although data on working after 1972 were not available. CONCLUSIONS: Confident interpretation is not possible but occupational exposures to hexavalent chromium may well have been involved in the increased mortality from lung cancer found in this cohort of chrome platers.

Aged↗