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PubMed2004

Layer-by-layer assembly of ordinary and composite coordination multilayers.

Coordination self-assembly of bishydroxamate-based metal-organic multilayers on gold employing a layer-by-layer (LbL) approach was investigated. It is shown that the solution chemistry of the participating metal ion has a marked influence on the composition and properties of the multilayers. Use of Ce4+ and particularly zirconium(IV) acetylacetonate (Zr(acac)4) solutions in the ion-binding step of multilayer construction leads to multilayers with a near-stoichiometric metal ion-to-ligand ratio, suggesting a structure close to that predicted by a simple coordination self-assembly scheme. On the other hand use of a ZrCl4 solution as the source of metal ions in the multilayer construction leads to a multilayer with greater thickness and a large excess of Zr(IV), evenly distributed between the organic layers. In the latter case, a ratio of ca. 1:2 between the excess Zr and oxygen, as well as long-term Zr4+ binding experiments showing deposition of ZrO2, suggest the formation of a zirconia-type nanophase between the bishydroxamate organic repeat units during multilayer self-assembly. Hence, while the multilayer prepared using Zr(acac)4 solution appears to represent a "true" coordination-based structure, the one prepared using ZrCl4 is best described as a composite organic-ceramic multilayer. Composite multilayers prepared in this way display different properties from those of the stoichiometric ones, such as improved dielectric behavior and higher stiffness. Even greater mechanical stability is obtained with multilayers constructed using alternate binding of ZrCl4 and Ce4+. The concept of LbL formation of coordination-based composite organic-ceramic structures may be useful in obtaining nanometer-scale structures with tunable properties.

Cesium↗
PubMed2001

Asymmetric total synthesis of (-)-alpha-kainic acid using an enantioselective, metal-promoted ene cyclization.

[figure: see text] A short and efficient asymmetric total synthesis of the title compound 1, which is an important neurotransmitter, has been achieved. The synthesis features a metal-promoted, enantioselective ene reaction that provides entry into the kainic acid ring system from very simple precursors. Moreover, the zirconium-mediated Strecker reaction, which represents an outgrowth of earlier amide-to-imine methodology developed in our laboratory, demonstrates remarkable chemoselectivity and stereoselectivity.

Excitatory Amino Acid Agonists↗
PubMed2001

Plaque formation on surface modified dental implants. An in vitro study.

Bacterial adhesion on titanium implant surfaces has a strong influence on healing and long-term outcome of dental implants. Parameters like surface roughness and chemical composition of the implant surface were found to have a significant impact on plaque formation. The purpose of this study was to evaluate the influence of two physical hard coatings on bacterial adhesion in comparison with control surfaces of equivalent roughness. Two members of the oral microflora, Streptococcus mutans and Streptococcus sanguis were used. Commercially pure titanium discs were modified using four different surface treatments: physical vapour deposition (PVD) with either titanium nitride (TiN) or zirconium nitride (ZrN), thermal oxidation and structuring with laser radiation. Polished titanium surfaces were used as controls. Surface topography was examined by SEM and estimation of surface roughness was done using a contact stylus profilometer. Contact angle measurements were carried out to calculate surface energy. Titanium discs were incubated in the respective bacterial cell suspension for one hour and single colonies formed by adhering bacteria were counted by fluorescence microscopy. Contact angle measurements showed no significant differences between the surface modifications. The surface roughness (Ra) of all surfaces examined was between 0.14 and 1.00 microm. A significant reduction of the number of adherent bacteria was observed on inherently stable titanium hard materials such as TiN and ZrN and thermically oxidated titanium surfaces compared to polished titanium. In conclusion, physical modification of titanium implant surfaces such as coating with TiN or ZrN may reduce bacterial adherence and hence improve clinical results.

Bacterial Adhesion↗
PubMed2003

Retention of prefabricated and individually cast root canal posts in vitro.

OBJECTIVES: The aim of the study was to evaluate the retention of prefabricated root canal posts made of a variety of materials that have recently been introduced into dentistry. MATERIALS AND METHODS: The posts studied were CosmoPost, Composipost carbon fibres, Composipost Aestheti-Plus, Composipost Light-Post and Para Post Fiber White. The posts were luted in extracted human premolars and the cores were built up with the resin composites recommended by the manufacturers. The retention of individually cast gold alloy posts luted with zinc-phosphate cement were used as reference. A universal testing machine was used to determine the retention of each cemented post Data were compared using ANOVA supplemented with Fisher's PLSD at a significance level of p < 0.05. RESULTS: Only the CosmoPost system exhibited retention values that were significantly lower than for the conventionally cast gold alloy posts luted with zinc-phosphate cement The force necessary to loosen the CosmoPost specimens was significantly less than that needed to loosen the Composipost. Estheti-Plus (p < 0.05) and the Composipost Ught-Post systems (p < 0.001]. The force necessary to loosen the ParaPost Fiber White specimens was significantly less than for the Composipost Light-Post system (p < 0.01). Other combinations did not differ significantly (p > 0.05). CONCLUSIONS: When zirconium oxide ceramic posts are luted with resin composites the bonding between the ceramic and resin composite seems to be weak. Further studies are thus necessary to achieve improved retention of all-ceramic root canal posts.

Analysis of Variance↗
PubMed2005

Superoxide radical anions on the surface of zirconia and sulfated zirconia: formation mechanisms, properties and structure.

In situ ESR spectroscopy has been used for direct comparison of different thermal and light-induced processes leading to generation of superoxide radical anions on the surface of various zirconia and sulfated zirconia materials. For materials of both types the magnetic resonance parameters of the radical anions were found to be practically independent of the generation method, except for oxygen coadsorption with NO that yields radicals with somewhat smaller gz values. The parameters appear to depend mostly on the state of the surface zirconia cations stabilizing the radical anions, so that the g tensor anisotropy is significantly smaller over sulfated zirconia. It is shown that light-induced formation of superoxide radical anions in the presence of coadsorbed hydrocarbons can be initiated with visible light. Original SIET reaction mechanisms are suggested for the formation of superoxide radical anions by coadsorption with hydrocarbons and illumination after such coadsorption to extend the previously known ones to account for the observed phenomena. Cluster model DFT calculations of magnetic resonance parameters of O2- radical anions stabilized on the surface of zirconium dioxide showed that the adsorption complexes have a -shape rather than linear structure. The magnetic resonance parameters obtained by calculations practically match experimental data and adequately describe their changes after the surface modification with sulfates.

Computer Simulation↗
PubMed2006

Muon spin relaxation study of Zr(H2PO4)(PO4).2H2O.

Muon spin relaxation has been used to study the muon dynamics in the layered zirconium phosphate Zr(H(2)PO(4))(PO(4)).2H(2)O as a function of temperature. Radiofrequency decoupling was used to establish the origin of the local dipolar field as coupling with (1)H spins. Muons were trapped at two sites, one identified as HMuO and the other consistent with PO-Mu on the basis of their zero-field second moments. Although a small decrease in the local nuclear dipolar field was seen with temperature, the muons remained essentially static over the temperature range 20-300 K.

Mesons↗
PubMed2004

An efficient and general route to reduced polypropionates via Zr-catalyzed asymmetric CC bond formation.

An efficient and general method for the synthesis of reduced polypropionates has been developed through the application of asymmetric carboalumination of alkenes catalyzed by dichlorobis(1-neomenthylindenyl)zirconium [(NMI)(2)ZrCl(2)]. In this investigation, attention has been focused on those reduced polypropionates that are alpha-monoheterofunctional and either omega-ethyl or omega-n-propyl. The reaction of 3-buten-1-ol with triethylaluminum (Et(3)Al) or tripropylaluminum ((n)Pr(3)Al) in the presence of (NMI)(2)ZrCl(2) and isobutylaluminoxane gave, after protonolysis, (R)-3-methyl-1-pentanol as well as (R)- and (S)-3-methyl-1-hexanols in 88-92% yield in 90-92% enantiomeric excess in one step. These 3-monomethyl-1-alkanols were then converted to two stereoisomers each of 2,4-dimethyl-1-hexanols and 2,4-dimethyl-1-heptanols via methylalumination catalyzed by (NMI)(2)ZrCl(2) and methylaluminoxane followed by oxidation with O(2). The four-step (or three-isolation-step) protocol provided syn-2,4-dimethyl-1-alkanols of >/=98% stereoisomeric purity in approximately 50% overall yields, whereas (2S,4R)-2,4-dimethyl-1-hexanol of comparable purity was obtained in 40% overall yield. Commercial availability of (S)-2-methyl-1-butanol as a relatively inexpensive material suggested its use in the synthesis of (2S,4S)- and (2R,4S)-2,4-dimethyl-1-hexanols via a three-step protocol consisting of (i) iodination, (ii) zincation followed by Pd-catalyzed vinylation, and (iii) Zr-catalyzed methylalumination followed by oxidation with O(2). This three-step protocol is iterative and applicable to the synthesis of reduced polypropionates containing three or more branching methyl groups, rendering this method for the synthesis of reduced polypropionates generally applicable. Its synthetic utility has been demonstrated by preparing the side chain of zaragozic acid A and the C11-C20 fragment of antibiotics TMC-151 A-F.

Carbon↗
PubMed1997

Polyvalent cationic metals induce the rate of transferrin-independent iron acquisition by HL-60 cells.

The trivalent metals iron, aluminum, and gallium greatly increase the rate of iron acquisition from low molecular weight chelates by human myeloid cells. The present study explores the mechanism responsible. Gallium-induced iron acquisition was shown to lead to stable cellular association of iron, the magnitude of which varied with the chelate to which the iron was bound. The majority of this iron initially associated with the plasma membrane. Cellular depletion of ATP did not affect the response to gallium nor did it require the continued presence of extracellular gallium. However, continued cell association of gallium was needed as subsequent cellular exposure to metal chelators resulted in a rapid loss of the "induced" phenotype. Other trivalent metals (lanthanum and gadolinium) and tetravalent metals (tin and zirconium) but not divalent metals also induced iron acquisition. Neither enhanced iron reduction nor protein kinase C or tyrosine kinases appeared involved in gallium-mediated induction of iron acquisition. Exposure of HL-60 cells to polyvalent cationic metals results in a dramatic and sustained increase in the rate of iron acquisition from low molecular weight chelating agents. This could be important for the rapid clearance of iron by phagocytes from the extracellular environment at sites of local tissue damage.

Adenosine Triphosphate↗
PubMed2006

Improved wear performance with crosslinked UHMWPE and zirconia implants in knee simulation.

BACKGROUND: Suggestions for improved wear performance of total knee replacements have included replacement of standard CoCr femoral components with ceramic and replacement of 3.5-Mrad ultra-high molecular weight polyethylene (UHMWPE) inserts with 5- or 7-Mrad UHMWPE inserts. The ceramic materials used clinically have included alumina, zirconia ceramic and oxidized zirconium. PATIENTS AND METHOD: We compared both CoCr and zirconia versions of the Bi-Surface knee replacement in a 6-station knee simulator using alpha calf serum for lubrication (20 mg protein per mL) to evaluate the relative bearing performance. RESULTS: We studied the 4-way knee simulation of implant materials: zirconia ceramic, CoCr, 3.5-Mrad UHMWPE, and 7-Mrad UHMWPE. With CoCr femoral components, the 7-Mrad UHMWPE resulted in a 5- to 8-fold reduction in wear compared to the 3.5-Mrad insert. With the 3.5-Mrad insert, the zirconia bearing provided approximately 4-fold wear reduction compared to CoCr. These wear rates with standard UHMWPE were similar to published wear studies on entire knees. With the exception of the CoCr/7-Mrad and ZrO2/3.5-Mrad combinations, the wear differences were statistically significant. INTERPRETATION: The ZrO2/7-Mrad UHMWPE combination gave the best performance, with no measurable wear over the 5.5 million cycle test duration.

Arthroplasty, Replacement, Knee↗
PubMed2002

Thermoluminescent response of ZrO2 + PTFE prepared in Mexico to 90Sr/90Y beta particles.

Results of studying the thermoluminescent response of undoped ZrO2 + PTFE pellets irradiated with 90Sr/90Y beta particles are presented. Previously, TL characteristics of ZrO2 films doped with rare earths were studied. Phosphor powder was obtained by evaporating a solution of zirconium nitrate in ethanol. In order to stabilise the traps in ZrO2 this phosphor was submitted to different thermal treatments. Optimal thermal treatment consisted in heating at 1100 degrees C for 24 h. With this powder. pressing at room temperature a mixture (2:1) of ZrO2 and polytetrafluoroethylene (PTFE), pellets of 5 mm diameter and 0.8 mm thickness were made. The glow curve of ZrO2 + PTFE pellets exhibited two peaks at 200 and 250 degrees C: its TL response as a function of beta particles dose was linear in the range from 2 to 60 Gy. Repeatability over 10 cycles was 1.8%. Fading at room temperature was 3.8% per month.

Beta Particles↗
PubMed2003

New contrast media designed for x-ray energy subtraction imaging in digital mammography.

RATIONALE AND OBJECTIVES: In contrast-enhanced dual-energy subtraction imaging 2 images acquired postcontrast media administration at different energies are subtracted to highlight structures hidden in the absence of contrast media. X-ray spectra of the newly developed digital full-field mammography units (GE Senographe 2000 D) are dominated by the emission lines of the Mo or Rh anodes. The K-edge of Zirconium (Zr) is flanked by these 2 emission lines. Thus, the attenuation of Zr should experience a pronounced change of attenuation in parallel with a change of anodes. Under clinically relevant conditions, the contrasting behavior of Zr should be compared with that of other elements having K-edge energies outside the window spanned by the 2 anode emission lines. METHODS: Solutions containing the contrasting elements Br, Y, Zr, I, and Gd were investigated for dual-energy subtraction in digital mammography with the 2 anode/filter settings (Mo/Mo and Rh/Rh). These solutions were investigated in phantom studies in the energy range conventionally used in mammography. Additionally, the contrasting behavior of Zr and I was compared in an in vivo study in rats. RESULTS: The sweeping over the K-edge by alternating between the Mo and Rh anodes increases the detection of Zr in energy subtraction imaging at constant high voltage. This procedure does not lead to sufficient contrast enhancement for iodine-based contrast media which become detectable by increasing the high voltage to 40-49 kV. CONCLUSION: The instrumental and physical data outlined predestine Zr as contrasting element with a high potential for energy subtraction imaging in digital mammography in the energy range conventionally applied.

Animals↗
PubMed2002

Narrowband impedance matching layer for high efficiency thickness mode ultrasonic transducers.

A new matching layer design concept has been proposed for narrowband continuous wave (CW) devices. Analysis has shown that the mechanical impedance of a resonant-type transducer in thickness mode CW operation does not equal its acoustic impedance rhoVs but roughly equals rhoVs/Q, where p is density, Vs is acoustic velocity, and Q is the mechanical quality factor. The value of rhoVs/Q is much lower than the acoustic impedance of water for any transducer material, including lead zirconium titanate (PZT), single crystals, or polyvinylidene fluoride (PVDF). With this new approach, the impedance of the matching layer must also be between water and pVs/Q, but there are few such practical low impedance materials. To realize equivalent low impedance structure, a novel double layer design is presented: a relatively low impedance material (such as polyethylene or polyurethane) on the inside and a relatively high impedance material (such as polyester or metal) on the outside. A high power CW transducer structure was designed and fabricated with PVDF-TrFE (polyvinylidene fluoride trifluoroethylene) to operate at 1.4 MHz. The basic quarter wavelength resonator structure is 0.7-mm alumina/0.2-mm piezo-polymer/0.25-mm polyester, and the matching section is 0.2-mm polyurethane and 0.25-mm polyester. A maximum power output of 6 to 9 W/cm2 with conversion efficiency of 30 to 35% was observed. For the transducer without matching section, the observed power was 3 to 4 W/cm2. Mason's model analyses (1) predict that the traditional matching layer is for broadband purposes and reduces output power both for PZT and PVDF-TrFE (2); this new matching scheme can be applied to PZT high power transducer. This high efficiency technique has application in various CW systems, such as Doppler sensors, interferometry, phase-sensitive imaging, or high energy focused beam systems.

Aluminum↗
PubMed1987

Effects of topically-applied antiperspirant on sweat gland function.

In subjects exposed to a hot environment, short-term topical pretreatment with aluminium zirconium tetrachlorhydrate delayed the onset of visible sweating although it failed to prevent the response. The delay was considered most probably to be due to the occlusive action, in the duct within the upper epidermis, of aluminium-containing conglomerates, which disappear after continuous sweating. However, microanalytical evidence indicated that ionic transport within the fundus secretory cells was also modified.

Administration, Topical↗
PubMed2006

Fracture resistance of single-tooth implant-supported all-ceramic restorations after exposure to the artificial mouth.

The purpose of this in vitro study was to evaluate the fracture resistance of single-tooth implant-supported all-ceramic restorations, composed of zirconium dioxide all ceramic restorations on different implant abutments, and to identify the weakest component of the restorative system. Forty-eight standardized maxillary central incisor zirconia crowns (Procera) were fabricated for two test groups and one control group (group Al: alumina abutments; group Zr: zirconia abutments; control group Ti: titanium abutments). All abutments were placed on the implants (Replace) using titanium screws. The crowns were adhesively luted using a resin luting agent (Panavia 21) and artificially aged through dynamic loading and thermal cycling. Afterwards, all specimens were tested for fracture resistance using compressive load on the palatal surfaces of the crowns. Pair-wise Wilcoxon rank tests were performed to test for differences in fracture resistance values with a global significance level of 0.05. All test specimens survived aging in the artificial mouth. No screw loosening was recorded. The median fracture resistance was 1251, 241 and 457 N for groups Ti, Al and Zr respectively. Statistically significant differences were found for the comparisons of group Ti with groups Al and Zr (P < 0.00001), and for the comparison of group Al with Zr (P < 0.00001). Results of this study showed that all tested implant-supported restorations have the potential to withstand physiological occlusal forces applied in the anterior region. Because of the low fracture resistance values of group Al, the combination of zirconia crowns and alumina abutments should carefully be considered before clinical application.

Aluminum Oxide↗
PubMed1977

A radioisotope dilution assay for unlabelled vitamin B12-intrinsic factor complex employing the binding intrinsic factor antibody: probable evidence for two types of binding antibody.

A new radioisotope dilution assay for vitamin B12-intrinsic factor complex is described. The method is based on the use of the binding type intrinsic factor antibody (the binding reagent), which when combined with the intrinsic factor-vitamin B12 complex (labelled ligand), is quantitatively adsorbed onto zirconium phosphate gel at pH 6.25. The new assay has been shown to provide a measure of intrinsic factor comparable with other intrinsic factor assays, but it has the important advantage of being able to measure the unlabelled vitamin B12-intrinsic factor complex (unlabelled ligand), and will, therefore, be valuable in the study of physiological events in the gastrointestinal tract. During the study, it was found that there is some evidence for a least two types of binding intrinsic factor antibody: One which combines preferentially with the intrinsic factor-vitamin B12 complex and one which combines equally well with this complex or with free intrinsic factor.

Antibodies↗
PubMed2005

The influence of ammonia and carbon dioxide on the sorption of a basic organic pollutant to a mineral surface.

UNLABELLED: Indoor surfaces have a sorptive capacity for organic pollutants which may be significantly influenced by other gases and the pH of the surface. In this research, we examine the influence of a common indoor gaseous acid, CO2, and base, NH3, on the adsorption of a volatile organic base, trimethylamine (TMA), to a mineral surface, zirconium silicate beads. Varying ammonia and CO2 within concentration ranges of indoor relevance substantially influences the sorptive capacity of this mineral surface. Increasing the CO2 mixing ratio to 1000 p.p.m. enhances surface capacity of TMA by 40-50%; increasing the NH3 mixing ratio to 10 p.p.m. decreases the TMA surface capacity by approximately 5-80% depending on relative humidity. The phenomena of dissolution of TMA into bulk surface water and acid-base chemistry in the surface water do not adequately describe equilibrium adsorption on this surface. Instead, adsorption to the dry solid or to adsorbed water layers appears to dominate. Reduction in the equilibrium partition coefficient, ke, in the presence of NH3 is due to a competition between TMA and ammonia molecules for adsorption sites. Site competition appears to follow the Langmuir competitive model and most ke values range from 0.003-0.045 m. PRACTICAL IMPLICATIONS: Sorptive interactions with indoor surfaces strongly influence indoor exposure to pollutants. For basic or acidic compounds, these interactions are themselves influenced by surface pH and competition with other acidic or basic gases such as CO2 and NH3. We show that CO2 tends to cause mineral surfaces to store more amines but NH3 tends to decrease this surface capacity. Given the typical range of indoor CO2 and NH3 concentrations, the indoor sorbtive capacity of amines on mineral surfaces may vary by greater than an order of magnitude.

Adsorption↗
PubMed2004

Do different implant surfaces exposed in the oral cavity of humans show different biofilm compositions and activities?

Osseointegrated dental implants play an important role in restorative dentistry. However, plaque accumulation may cause inflammatory reactions around the implants, sometimes leading to implant failure. In this in vivo study the influence of two physical hard coatings on bacterial adhesion was examined in comparison with a pure titanium surface. Thin glass sheets coated with titanium nitride (TiN), zirconium nitride (ZrN) or pure titanium were mounted on removable intraoral splints in two adults. After 60 h of intraoral exposure, the biofilms were analyzed to determine the number of bacteria, the types of bacteria [by applying single-strand conformation polymorphism (SSCP analysis) of 16S rRNA genes], and whether or not the bacteria were active (by SSCP analysis of 16S rRNA). The results showed that bacterial cell counts were higher on the pure titanium-coated glass sheets than on the glass sheets coated with TiN or ZrN. The lowest number of bacterial cells was present on theZrN-coated glass. However, the metabolic activity (RNA fingerprints) of bacteria on TiN- and ZrN-coated glass sheets seemed to be lower than the activity of bacteria on the titanium-coated surfaces, whereas SSCP fingerprints based on 16S rDNA revealed that the major 16S bands are common to all of the fingerprints, independently of the surface coating.

Adult↗
PubMed2005

Clinical fit of all-ceramic three-unit fixed partial dentures, generated with three different CAD/CAM systems.

In this study, the hypothesis was tested that the marginal and internal fit of CAD/CAM fabricated all-ceramic three-unit fixed partial dentures (FPDs) can be as good as in metal-ceramic FPDs. Twenty-four all-ceramic FPDs were fabricated and randomly subdivided into three equally sized groups. Eight frameworks were fabricated using the Digident CAD/CAM system (DIGI), another eight frameworks using the Cerec Inlab system (INLA). Vita Inceram Zirkonia blanks were used for both groups. In a third group frameworks were milled from yttrium-stabilized Zirconium blanks using the Lava system (LAVA). All frameworks were layered with ceramic veneering material. In addition, six three-unit metal-ceramic FPDs served as control group. All FPDs were evaluated using a replica technique with a light body silicone stabilized with a heavy body material. The replica samples were examined under microscope. The medians of marginal gaps were 75 microm for DIGI, 65 microm for LAVA and INLA and 54 microm for the conventional FPDs. Only the DIGI data differed significantly from those of the conventional FPDs. Within the limits of this study, the results suggest that the accuracy of CAD/CAM generated three-unit FPDs is satisfactory for clinical use.

Aluminum Oxide↗