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Chromosomal alterations and sister chromatid exchanges induced by zirconium oxychloride in human lymphocytes in vitro with relation to age of donors.

Aqueous solutions of zirconium oxychloride were added to human peripheral blood lymphocyte culture. Cultures were set up from healthy donors of both sexes belonging to age groups of 0-10, 11-20, 21-30, 31-40, 41-50 and 51-60 years. Airdried Giemsa schedule was followed for preparation of chromosomal aberrations and micronuclei count. Flourescence plus Giemsa staining techniques were applied for the study of sister chromatid exchange. The endpoints screened were chromosome and chromatid breaks, dicentrics and rearrangements. The frequencies of chromosomal aberrations and sister chromatid exchanges induced were compared between the samples of different age groups. The frequency of CA could not be related to age of the donor. However, the frequency of SCE increased with increase in age of female donor.

Adolescent↗

Cytotoxic effects of zirconium oxychloride on bone marrow cells of mice.

A single oral administration of an aqueous solution of zirconium oxychloride to mice of both sexes in concentrations 1/20, 1/6, 1/2 of LD50 induced chromosomal abnormalities in bone marrow cells. The frequencies of aberration were directly proportionate to the concentrations used. Female mice were found to be more susceptible than male mice, though not to a significantly higher level. This is the first report on the clastogenicity of this metal.

Animals↗

Mitogenic effects of beryllium and zirconium salts on mouse splenocytes in vitro.

The beryllium (Be) and zirconium (Zr) salts, BeSO4 and Zr(SO4)2, each exerted a concentration-dependent stimulation of mouse spleen cell proliferation as measured by an increase in [3H]thymidine incorporation into lymphocyte DNA, although the maximal response induced by Zr(SO4)4 (4-5 fold at 100-200 microM) was greater than that by BeSO4 (2-3 fold at 1-5 microM). Preincubation of splenocytes with low concentrations of BeSO4 (less than 1 microM) or a broad range of Zr(SO4)2 concentrations (2-100 microM) was also found to assist subsequent lectin (concanavalin A; ConA)-mediated lymphocyte proliferation. The results indicate that at defined concentrations Be and Zr salts can both act as lymphocyte mitogens and augment the functional responsiveness of immune cells, which may help explain the characteristic induction of delayed hypersensitivity and production of immunological granulomas by these metals in vivo.

Animals↗

Relationship of clastogenic effects of zirconium oxychloride to dose and duration of exposure in bone marrow cells of mice in vivo.

Zirconium oxychloride was administered as a single oral dose to laboratory-bred Swiss albino mice corresponding to 1/2, 1/6 and 1/20 of the LD50 values. Bone marrow cells were screened after 6, 12 and 24h for chromosomal aberrations following an air-drying-Giemsa schedule. The frequencies of chromosomal breaks and alterations induced increased significantly at a rate directly proportional to the concentration used. The increase was also related to the period after exposure, although to a less extent than the concentration used. No direct relationship could be observed to the sex of the animal.

Administration, Oral↗

Zirconium molybdate gel as a generator for technetium-99m--I. The concept and its evaluation.

A new 99mTc generator for the preparation of radiopharmaceuticals has been developed. Its elution characteristics and chemical stability merit its consideration as a replacement for present generators. The 99Mo is present as a zirconium molybdate gel, the high molybdate content of which allows the use of (n, gamma) 99Mo. The resulting generator is as effective and as convenient to use as chromatographic generators that are based on fission product 99Mo. Laboratory evaluations of the concept at low levels of radioactivity described in this paper show that the gel can be prepared in a form which is stable when used in a generator and from which TcO4- can be eluted in yields of 80-85%. The influence of formulation variables on gel properties was established. The performance of this generator using 99Mo with specific activities between 4 and 13 GBq g-1 is described in a further paper.

Chemical Precipitation↗

A facile method for the labeling of proteins with zirconium isotopes.

To label proteins with positron emitters with a half-life in the order of days, a method has been developed to label proteins with zirconium (Zr)-isotopes. Therefore, the bifunctional chelating agent desferal (Df) was coupled to albumins via a thioether bond. Labeling of the premodified proteins was easily performed by addition of these proteins to freeze-dried Zr-oxalate. This labeling was efficient (> 90%) and accomplished in several minutes. The conjugates showed a high in vitro stability. Biodistribution studies were performed with 88Zr-citrate, 88Zr-Df, and 88Zr-labeled mouse serum albumin (88Zr-Df-MSA), modified with different amounts of chelating groups. Whereas Zr-citrate was found to accumulate in bone, Zr-Df was cleared very fast by glomerular filtration. The 88Zr-Df-MSA showed similar blood clearance as did 123I-labeled MSA. The biodistribution pattern of 88Zr-Df-MSA differed only from 123I-MSA in that a higher accumulation of Zr in liver, kidney, and spleen was found. The absence of large amounts of 88Zr in bone indicated that in vivo the conjugates are also reasonably stable.

Animals↗

Hydroxyapatite/titania sol-gel coatings on titanium-zirconium alloy for biomedical applications.

A simple sol-gel method was developed for hydroxyapatite/titania (HA/TiO(2)) coatings on non-toxic titanium-zirconium (TiZr) alloy for biomedical applications. The HA/TiO(2)-coated TiZr alloy displayed excellent bioactivity when soaked in a simulated body fluid (SBF) for an appropriate period. Differential scanning calorimetry, thermogravimetric analysis, X-ray diffraction and scanning electron microscopy-energy dispersive spectrometry were used to characterize the phase transformations and the surface structures and to assess the in vitro tests. The HA/TiO(2) layers were spin-coated on the surface of TiZr alloy at a speed of 3000rpm for 15s, followed by a heat treatment at 600 degrees C for 20min in an argon atmosphere sequentially. The TiO(2) layer exhibited a cracked surface and an anatase structure and the HA layer displayed a uniform dense structure. Both the TiO(2) and HA layers were 25microm thick, and the total thickness of the HA/TiO(2) coatings was 50microm. The TiZr alloy after the above HA/TiO(2) coatings displayed excellent bone-like apatite-forming ability when soaked in SBF and can be anticipated to be a promising load-bearing implant material.

Alloys↗

Immobilization of hemoglobin on zirconium dioxide nanoparticles for preparation of a novel hydrogen peroxide biosensor.

Direct electrochemistry and thermal stability of hemoglobin (Hb) immobilized on a nanometer-sized zirconium dioxide (ZrO2) modified pyrolytic graphite (PG) electrode were studied. The immobilized Hb displayed a couple of stable and well-defined redox peaks with an electron transfer rate constant of (7.90 +/- 0.93)s(-1) and a formal potential of -0.361 V (-0.12 V versus NHE) in 0.1M pH 7.0 PBS. Both nanometer-sized ZrO2 and dimethyl sulfoxide (DMSO) could accelerate the electron transfer between Hb and the electrode. Spectroscopy analysis of the Hb/ZrO2/DMSO film showed that the immobilized Hb could retain its natural structure. This modified electrode showed a high thermal stability up to 74 degrees C and an electrocatalytic activity to the reduction of hydrogen peroxide (H2O2) without the aid of an electron mediator. The electrocatalytic response showed a linear dependence on the H2O2 concentration ranging from 1.5 to 30.2 microM with a detection limit of 0.14 microM at 3sigma. The apparent Michaelis-Menten constant KMapp for H2O2 sensor was estimated to be (0.31 +/- 0.02) mM, showing a high affinity.

Biosensing Techniques↗

Evaluation of new surfactant expanded zirconium and titanium phosphates for polycyclic aromatic hydrocarbons extraction from waters.

A newly synthesized family of materials prepared with surfactant as organic template were tested for the extraction of polycyclic aromatic hydrocarbons (PAHs) from water, using pyrene (Pyr) and benzo[a]pyrene (B[a]P) as PAHs representatives. Particular attention was paid to the evaluation of the recovery factors with dichloromethane as eluent in order to estimate their potential as adsorbing solid phases for PAH remediation or analysis. Eleven lamellar MCM-50 type materials incorporating n-alkyl- (n = 12, 16, 18) trimethylammonium bromide molecules with different concentrations and chain lengths and two hexagonal MCM-41 type materials incorporating octadecyl-trimethyl ammonium bromide were tested. Best results were obtained by preparing lamellar MCM-50 zirconium and titanium phosphates in the presence of n-dodecyl-trimethylammonium at a relative molar concentration (surfactant/phosphate) of 1.

Absorption↗

Adsorption of anions to zirconium(IV) and titanium(IV) chemically immobilized on gel-phase.

Adsorption behaviors of 25 anions to zirconium(IV) and titanium(IV) chemically immobilized on a gel-phase were studied by ion chromatography and by batch adsorption experiments. The affinities of Zr(IV) to iminodiacetate as an anchoring group and to anions as a sample are much stronger than those of Ti(IV). On a Zr(IV) column, fourteen anions showed no retention, four anions showed pH-dependent retention in a low pH region, and seven anions were irreversibly adsorbed at pH <7. In the last group, fluoride was adsorbed both by the ligand exchange mechanism and the addition mechanism, while phosphate, arsenate and selenite were only by the ligand exchange mechanism. The structures of the adsorbed species are discussed.

Adsorption↗

Characterization of hemoglobin immobilized on gamma-zirconium phosphate.

The fact that different gamma-zirconium phosphate (gamma-ZrP) preintercalation method induced varied degree and type of conformational change of the adsorption protein was confirmed by characterization techniques including circular dichroism (CD), fourier transform infrared spectroscopy (FTIR) and X-ray powder diffraction (XRD) analysis. The results indicated that the association of hemoglobin with gamma-ZrP preintercalated using butylamine was correlated with conformational change in the secondary structure of the protein. gamma-ZrP which was preintercalated with tetra (n-butylammonium) hydroxide caused the conformational change of Hemoglobin in both the secondary structure and the tertiary structure. X-ray powder diffraction analysis was used to analyze the crystalline structure of the nanocomposites prepared by relamination. The adsorption isotherms of Hemoglobin on different matrices were set up and fitted with Langmuir and Freundlich equations.

Absorption↗

Microbial adhesion to zirconium alloys.

We present data and analyses concerning the adhesion of clinically relevant Staphylococcus aureus, Staphylococcus epidermidis, and Pseudomonas aeruginosa (bacteria) and Candida albicans (yeast) to Zircaloy-2 (Zry-2) and Zircadyne-705 (Zr705) surfaces. These zirconium-based materials are similar to those now being used in total hip and knee replacements. Here we study clinical strains of microbes under shaken and stationary exposure conditions, and their ability to adhere to Zr surfaces having different oxide thicknesses. We use X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), viable counts, endotoxin assays, and statistical analysis methods, and demonstrate a predictive model for microbial adhesion based on XPS data.

Alloys↗

Adsorption characteristics of various organic substances on the surfaces of tantalum, titanium, and zirconium.

Adsorption characteristics of carboxylic acids, amines, an octapeptide composed of four L-alanine and four L-aspartic acid residues (Peptide-A4D4), and beta-lactoglobulin (beta-Lg) on tantalum (Ta), titanium (Ti), and zirconium (Zr) particles were examined at 30 degrees C and in some case, were compared with their adsorption onto SUS316L stainless steel particles (S6L). The adsorption isotherms on the Ta, Ti, and Zr particles could usually be expressed either by a Langmuir-type equation for reversible adsorption or by a modified Langmuir-type adsorption equation including terms for both reversible and irreversible adsorption. The adsorption equilibrium of benzoic acid, benzylamine, and m-xylylenediamine on all the metal surfaces followed a Langmuir-type equation, while those of phthalic acid, mellitic acid, and Peptide-A4D4 could be fitted to the modified Langmuir-type adsorption equation. The adsorption characteristics of different adsorbates on the different surfaces were discussed particularly with reference to the pH dependencies of the q(irrev), q(rev), and K values and the electrostatic properties of the oxidized surface of the metal particles. Fourier transform infrared spectroscopic analyses using a reflection/absorption technique (RA-IR) indicated that phthalic acid and mellitic acid are adsorbed in similar adsorption states irrespective of the type of metal. beta-Lg was adsorbed onto the surfaces principally in an irreversible manner. The desorption behavior of beta-Lg from Ta, Ti, and S6L surfaces was examined, in order to evaluate the extent of interaction between beta-Lg and the metals.

Adsorption↗

Selective adsorption of phosphate from seawater and wastewater by amorphous zirconium hydroxide.

Phosphate adsorption from single electrolyte (NaH2PO4), phosphate-enriched seawater, and model wastewater was studied using amorphous zirconium hydroxide, ZrO(OH)2(Na2O)0.05 1.5H2O, as an adsorbent. Batch experiments were carried out to investigate the adsorption of phosphate. The effect of pH on phosphate adsorption from seawater showed that the uptake of phosphate increased with an increase in pH up to 6, and then decreased sharply with a further increase in pH of the solution. The equilibrium data of phosphate adsorption were followed with a Freundlich isotherm. The uptake of phosphate at the adsorbent/solution ratio 0.05 g/2 L was 10 and 17 mg-P/g for the phosphate-enriched seawater and the model wastewater, respectively. A much higher adsorptivity toward phosphate ions in seawater was observed on ZrO(OH)2(Na2O)0.05 1.5H(2)O than on other representative adsorbents based on layered double hydroxides of Mg(II)-Al(III), Mg(II)-Fe(III), and Ni(II)-Fe(III). The effective desorption of phosphate ions on ZrO(OH)2(Na2O)0.05 1.5H2O could be achieved using a 0.1 M NaOH solution. The usefulness of experimental data for practical applications in removing phosphate in seawater and wastewater is discussed.

Adsorption↗

Removal of Cd(II) from aqueous solution by kaolinite, montmorillonite and their poly(oxo zirconium) and tetrabutylammonium derivatives.

Kaolinite, montmorillonite and their poly(oxo zirconium) and tetrabutylammonium derivatives have been used in this work for removing Cd(II) from aqueous solution. Batch adsorption studies were carried out under various Cd(II) concentrations, amount of clay adsorbents, pH, interaction time and temperature. The uptake of the metal was initially very fast, but gradually slowed down indicating diffusion into the interior of the adsorbent particles. The adsorption processes were more akin towards second order reaction mechanism. The suitability of the adsorbent was tested by fitting the adsorption data with Langmuir and Freundlich isotherms, which gave good fits with both isotherms. Adsorption was poor in strongly acidic solution but was improved in alkaline medium and continuously increased with rise in pH. The values of the thermodynamic parameters, DeltaH, DeltaS and DeltaG, indicated the interactions to be thermodynamically favourable.

Adsorption↗

In vitro evaluation of shear bond strengths of resin to densely-sintered high-purity zirconium-oxide ceramic after long-term storage and thermal cycling.

STATEMENT OF PROBLEM: The few available studies on the resin bond to zirconium-oxide ceramic recommend airborne-particle abrasion and modified resin luting agents containing adhesive monomers for superior and long-term durable bond strengths. It is unknown whether this regimen can also be successfully applied to the intaglio surface of a commercial zirconia-based all-ceramic system. PURPOSE: The purpose of this study was to evaluate and compare bond strengths of different bonding/silane coupling agents and resin luting agents to zirconia ceramic before and after artificial aging. MATERIAL AND METHODS: Composite cylinders (2.9 mm x 3.0 mm) were bonded to airborne-particle-abraded intaglio surfaces of Procera AllZirkon specimens (n=80) with either Panavia F (PAN) or Rely X ARC (REL) resin luting agents after pretreatment with Clearfil SE Bond/ Porcelain Bond Activator (Group SE). In another group, Rely X ARC was used with its bonding/silane coupling agent (Single Bond/Ceramic Primer, Group SB). PAN without any bonding/silane agent (Group NO) was the control. Subgroups of 10 specimens were stored in distilled water for either 3 or 180 days before shear bond strength was tested. One hundred eighty-day-old specimens were repeatedly thermal cycled for 12,000 cycles between 5 and 60 degrees C with a 15-second dwell time. Data were analyzed with 1- and 2-way analysis of variance and the Tukey multiple comparisons test (alpha=.05). Failure modes were examined under original magnification x25. RESULTS: After 3 days, SE-REL (25.15 +/- 3.48 MPa) and SE-PAN (20.14 +/- 2.59 MPa) groups had significantly superior mean shear bond strengths (P=.0007) compared with either NO-PAN (17.36 +/- 3.05 MPa) or SB-REL (16.90 +/- 7.22 MPa). SE-PAN, NO-PAN, and SB-REL groups were not significantly different. Artificial aging significantly reduced bond strengths. After 180-day storage, SE-PAN (16.85 +/- 3.72 MPa), and SE-REL (15.45 +/- 3.79 MPa) groups demonstrated significantly higher shear bond strengths than NO-PAN (9.45 +/- 5.06 MPa) or SB-REL (1.08 +/- 1.85 MPa) groups. The modes of failure varied among 3-day groups but were 100% adhesive at the ceramic surfaces after artificial aging. CONCLUSION: Artificial aging significantly reduced bond strength. A bonding/silane coupling agent containing an adhesive phosphate monomer can achieve superior long-term shear bond strength to airborne-particle- abraded Procera AllZirkon restorations with either one of the 2 resin luting agents tested.

Bisphenol A-Glycidyl Methacrylate↗

Replacement of two mandibular central incisors using a zirconium resin-bonded fixed partial denture: a clinical report.

Maxillary and mandibular anterior tooth loss may cause esthetic and functional problems. Successful treatment for these situations may necessitate a minimally invasive technique to preserve sound remaining abutment tooth structure. This article describes the use of zirconium resin-bonded fixed partial denture as a conservative treatment option for the replacement of 2 mandibular central incisors.

Adult↗

The efficacy of posterior three-unit zirconium-oxide-based ceramic fixed partial dental prostheses: a prospective clinical pilot study.

STATEMENT OF PROBLEM: Although zirconium-oxide-based restorations for fixed partial denture prostheses (FPDPs) are available for use, clinical studies evaluating their longevity and related complications have not been published. PURPOSE: The aim of this pilot clinical study was to assess the efficacy of zirconia-based posterior 3-unit FPDPs. MATERIAL AND METHODS: Twenty 3-unit posterior FPDPs (Lava) were placed in 16 subjects who were missing a second premolar or a first molar, met specific inclusion and exclusion criteria, and provided informed consent. All teeth were prepared in a standardized manner: occlusal reduction of 1.5 to 2 mm; axial reduction of 1 to 1.5 mm; a 1.0-mm, 360-degree rounded shoulder placed 0.5 mm subgingivally on the facial aspect and supragingivally on the lingual aspect on sound tooth structure; and rounded internal line angles. Impressions were made with vinyl polysiloxane (Express) impression material. Frameworks were fabricated using a computer-aided design/computer-assisted manufacturing technique with a retainer thickness of 0.6 mm, and a minimal connector surface area of 9 mm(2). Restorations were luted with resin-modified glass-ionomer cement (Rely X luting). Recall appointments were made after 2 weeks and 6, 12, 18, 24, and 36 months. Clinical fracture resistance, marginal discoloration, marginal adaptation, radiographic proximal recurrent decay, and periapical pathoses were assessed over time using modified Ryge criteria. The probability distributions of these variables were calculated for the baseline data as well as for recall data. RESULTS: Mean follow-up was 31.2 months. Fifteen restorations were rated Alpha in all measured parameters. Minor chipping of veneering porcelain was detected in 5 restorations rated Bravo for clinical fracture resistance and Alpha for all other assessed parameters. One restoration was rated Bravo in terms of marginal integrity at 36 months. CONCLUSIONS: Zirconia-based posterior 3-unit FPDPs performed well after short-term service.

Adult↗