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PubMed2006

Early biofilm colonization on polished- and glazed-zirconium ceramic surface. Preliminary results.

AIM: The purpose of this study was to evaluate the effect of ceramic surface polishing procedure on the early dental biofilm formation on zirconium ceramics. METHODS: Twenty samples (discs shape) of tetragonal zirconium polycrystal stabilized with yttrium ceramics (Y-TZP) for LAVA system were fabricated (5 mm diameter and 1.5 mm thickness). Two patients with high level of dental hygiene were selected for this study. Oral devices covering the crowns of the upper premolars and molars were fabricated for each participant. Glazed and polished samples of Y-TZP ceramics were fixed on the vestibular and palatal zones of the devices. After 20 min (8 samples) and 1 h (8 samples) in the oral environment, the samples were removed and analyzed in a scanning electron microscope. The surface topographies of 4 ceramic samples (2 glazed and 2 polished) were analyzed (control group: without exposition in oral environment). RESULTS: The glazed samples showed a more irregular surface than polished samples. Deposition of granular aggregates was verified on all the samples in the two times of the study analyzed. This granular material coated more intensely on irregular areas, and its thickness increased after 1 h. No difference was observed as to bacterial morphology in any time of the study. Cocci and rods-shaped prevailed. CONCLUSIONS: Glazed surfaces presented larger tendency to dental biofilm accumulation.

Adult↗
PubMed1985

Antitumor activity of 1.3-diketonato zirconium (IV) and hafnium (IV) complexes.

Ten six-coordinate dihalogenobis (1.3-diketonato)zirconium (IV) and hafnium (IV) complexes as well as seven halogenotris(1.3-diketonato) zirconium(IV) and hafnium(IV) species were prepared and characterized by their elemental analysis, IR- and NMR-spectra. Their antitumor activity was tested using the intraperitoneally transplanted Sarcoma 180 tumor system in mice. Cisplatin was used in several doses as positive control compound. Seven complexes were highly active. The ratio of median survival time of treated to untreated control animals ranged up to 3 (T/C = 300%; the experiment was interrupted after that time) for these compounds. Significance according to Kruskal-Wallis test, long-time survivors, and animals which are dead on day 5 and day 30 are given. The possible mechanism of action compared to cisplatin is discussed.

Animals↗
PubMed1976

[Granulomas of axillae (zirconium?) (author's transl)].

Deodorant preparations containing Zirconium may induce axillary granulomas of allergic origin. The case of a 49 years old female patient is presented, who developed axillary granulomas after having used a deodorant preparation containing Zirconium.

Axilla↗
PubMed2004

Zirconium-mediated coupling reactions of amines and enol or allyl ethers: synthesis of allyl- and homoallylamines.

An easy and efficient zirconium-mediated synthesis of allylamines from simple amines and enol ethers is described. This strategy also allows the synthesis of amino alcohol derivatives containing a Z double bond in their structure when 2,3-dihydrofuran is used. Simple conventional modification of these amino alcohols leads to 2-substituted piperidine derivatives. By applying this approach, a formal total synthesis of the alkaloid coniine is easily achieved from a protected butylamine. Finally, the zirconium-mediated reaction of amines and allyl phenyl ether furnishes homoallylamines or amino ethers depending on the structure of the starting amine.

Journal Article↗
PubMed2005

The zirconium alkoxide-catalyzed aldol-Tishchenko reaction of ketone aldols.

The aldol-Tishchenko reaction of ketone aldols as enol equivalents has been developed as an efficient strategy to furnish differentiated 1,3-anti-diol monoesters in one step. The thermodynamically unstable ketone aldols undergo a facile retro-aldolization to yield a presumed zirconium enolate in situ, which then undergoes the aldol-Tishchenko reaction in typically high yields and with complete 1,3-anti diastereocontrol. Evaluation of a broad range of metal alkoxides as catalysts and optimization of the reaction protocol led to a modified zirconium alkoxide catalyst with attenuated Lewis acidity and dichloromethane as solvent, which resulted in suppression of the undesired acyl migration to a large extent. Various ketone aldols have been prepared and subjected to the general process, giving rise to a broad range of differently substituted 1,3-anti-diol monoesters, which may be hydrolyzed to the corresponding 1,3-anti-diols.

Journal Article↗
PubMed2007

Chiral fluorous dialkoxy-diamino zirconium complexes: synthesis and use in stereospecific polymerization of 1-hexene.

New catalysts for the isospecific polymerization of 1-hexene based on cationic zirconium complexes incorporating the tetradentate fluorous dialkoxy-diamino ligands [OC(CF(3))(2)CH(2)N(Me)(CH(2))(2)N(Me)CH(2)C(CF(3))(2)O](2-) [(ON(2)NO)(2-)] and [OC(CF(3))(2)CH(2)N(Me)(1R,2R-C(6)H(10))N(Me)CH(2)C(CF(3))(2)O](2-) [(ON(Cy)NO)(2-)] have been developed. The chiral fluorous diamino-diol [(ON(Cy)NO)H(2), 2] was prepared by ring-opening of the fluorinated oxirane (CF(3))(2)COCH(2) with (R,R)-N,N'-dimethyl-1,2-cyclohexanediamine. Proligand 2 reacts cleanly with [Zr(CH(2)Ph)(4)] and [Ti(OiPr)(4)] precursors to give the corresponding dialkoxy complexes [Zr(CH(2)Ph)(2)(ON(Cy)NO)] (3) and [Ti(OiPr)(2)(ON(Cy)NO)] (4), respectively. An X-ray diffraction study revealed that 3 crystallizes as a 1:1 mixture of two diastereomers (Lambda-3 and Delta-3), both of which adopt a distorted octahedral structure with trans-O, cis-N, and cis-CH(2)Ph ligands. The two diastereomers Lambda-3 and Delta-3 adopt a C(2)-symmetric structure in toluene solution, as established by NMR spectroscopy. Cationic complexes [Zr(CH(2)Ph)(ON(2)NO)(THF)(n)](+) (n=0, anion=[B(C(6)F(5))(4)](-), 5; n=1, anion=[PhCH(2)B(C(6)F(5))(3)](-), 6) and [Zr(CH(2)Ph)(ON(Cy)NO)(THF)](+)[PhCH(2)B(C(6)F(5))(3)](-) (7) were generated from the neutral parent precursors [Zr(CH(2)Ph)(2)(ON(2)NO)] (H) and [Zr(CH(2)Ph)(2)(ON(Cy)NO)] (3), and their possible structures were determined on the basis of (1)H, (19)F, and (13)C NMR spectroscopy and DFT methods. The neutral zirconium complexes H and 3 (Lambda-3/Delta-3 mixture), when activated with B(C(6)F(5))(3) or [Ph(3)C](+)[B(C(6)F(5))(4)](-), catalyze the polymerization of 1-hexene with overall activities of up to 4500 kg PH mol Zr(-1) h(-1), to yield isotactic-enriched (up to 74 % mmmm) polymers with low-to-moderate molecular weights (M(w)=4800-47 200) and monodisperse molecular-weight distributions (M(w)/M(n)=1.17-1.79).

Journal Article↗
PubMed1997

Growth and Structure of Zirconium Hydrous Polymers in Aqueous Solutions

Zirconium oxychloride solutions prepared at different pH were heated at elevated temperatures for various aging periods to gain an understanding of the growth mechanism and structure of zirconium hydrous polymers. Small angle X-ray scattering (SAXS) measurements were made on these solutions. It was observed that shape of clusters at the earlier stages of growth is close to a rod rather than a sheet as suggested earlier. The scattering data indicate that a rod-shaped primary particle is formed at pH 1.2, and on an increase in the pH, the primary particles become more branched. On aging more than 1250 min at 92°C, these primary particles form large aggregates while retaining the primary particle structure. These aggregates, which are mass fractal in nature, restructure while growing in size and eventually transform into dense particles. Scattering data in this study were not enough to determine a specific kinetic growth model of the aggregates because the scattering intensity at low q constantly changes with time during the restructuring process. Copyright 1997 Academic Press. Copyright 1997Academic Press

Journal Article↗
PubMed2002

Sol-gel derived carbon ceramic electrode containing methylene blue-intercalated alpha-zirconium phosphate micro particles.

Methylene blue-intercalated alpha-zirconium phosphate (MBZrP) micro particles in deionized water were deposited onto the surface of graphite powder to prepare graphite powder-supported MBZrP, which was subsequently dispersed into methyltrimethoxysilane-derived gels to yield a conductive composite. The composite was used as electrode material to fabricate a surface-renewable, rigid, leak-free carbon ceramic composite electrode, bulk-modified with methylene blue (MB). In the configuration, alpha-zirconium phosphate was employed as a solid host for MB, which acted as a catalyst. Graphite powder ensured conductivity by percolation, the silicate provided a rigid porous backbone and the methyl groups endowed hydrophobicity and thus limited the wetting section of the modified electrode. Peak currents of the MBZrP-modified electrode were surface-confined at low scan rates but diffusion-controlled at high scan rates. Square-wave voltammetric study revealed that MBZrP immobilized in carbon ceramic matrix presented a two-electron, three-proton redox process in acidic aqueous solution with pH ranged from 0.44 to 2.94. In addition, the chemically modified electrode showed an electrocatalytic activity toward nitrite reduction at +0.15 V ( vs. Ag/AgCl) in acidic aqueous solution (pH=0.44). The linear range and detection limit are 1x10(-6)-4x10(-3) mol x L(-1) and 1.5x10(-7) mol x L(-1), respectively.

Journal Article↗
PubMed2004

Synthesis, characterization, and analytical application of zirconium(IV) selenoiodate, a new cation exchanger.

Zirconium(IV) selenoiodates have been synthesized under a variety of conditions. The most chemically and thermally stable sample is prepared by adding a mixture of aqueous solutions of 0.1 mol L(-1) potassium iodate and 0.1 mol L(-1) sodium selenite to aqueous solution of 0.1 mol L(-1) zirconium(IV) oxychloride. Its ion-exchange capacity for K+ and Pb2+ was found to be 3.20 and 2.35 meq g(-1) dry exchanger, respectively. The material has been characterized on the basis of chemical composition, pH titration, and thermogravimetric analysis. The effect on the exchange capacity of drying the exchanger at different temperatures has also been studied. The analytical importance of the material has been established by quantitative separation of Pb2+ from other metal ions.

Journal Article↗
PubMed2004

Separation of 90Y from 90Sr using zirconium vanadate as the ion exchanger.

The sorption and desorption behaviour of several radionuclides, including 241Am, 152,154Eu, 233U, 137Cs, 90Sr and 90Y was studied under varying acidities using zirconium vanadate as ion exchanger. The sorption follows the order: Cs > Eu > Am >Y > U, while Sr was not taken up by the ion exchanger. A radiochemical separation scheme for the 90Y daughter from its 90Sr parent using zirconium vanadate ion exchanger has been developed. The exchanger was synthesized and characterized in our laboratory.

Journal Article↗
PubMed2005

Separation of (134)Cs and (152)Eu using inorganic ion exchangers, zirconium vanadate and ceric vanadate.

Two inorganic ion exchangers, zirconium vanadate and ceric vanadate were synthesized and applied to confine and separate (152)Eu and (134)Cs from a synthetic mixture. The percentages of adsorption of the two radionuclides were studied for the two ion exchangers at varying pH conditions. At pH 3, zirconium vanadate adsorbs both Eu and Cs and a column chromatographic separation was achieved using 0.1M EDTA as the eluant. The ceric vanadate ion exchanger showed an increased trend in adsorption for both the radionuclides with increase of pH value from 1 to 6. At pH 1, a column chromatographic separation of these radionuclides from a mixture was achieved, because at this pH only (134)Cs was adsorbed to ceric vanadate bed in the column.

Journal Article↗
PubMed2000

Ion-chromatographic behavior of alkali metal cations and ammonium ion on zirconium-adsorbing silica gel.

The preparation and evaluation of zirconium-adsorbing silica gel (Zr-Silica) as an ion-exchange stationary phase in ion chromatography for inorganic anions and cations was carried out. The Zr-Silica was prepared by the reaction of silanol groups on the surface of the silica gel with zirconium butoxide (Zr(OCH2CH2CH2CH3)4) in ethanol. The ion-exchange characteristics of the Zr-Silica were evaluated using 10 mM tartaric acid at pH 2.5 as eluent. The Zr-Silica was found to act as a cation-exchanger under the eluent conditions. The retention behavior of alkali and alkaline earth metal cations was then investigated. The Zr-Silica column was proved to be suitable for the simultaneous separation of alkali metal cations and ammonium ion. Excellent separation of the cations on a 15 cm Zr-Silica column was achieved in 25 min using 10 mM tartaric acid as eluent.

Alkalies↗
PubMed2003

Synthesis, structural investigation, and solid-state properties of iodine-doped zirconium diphthalocyanine, [ZrPc2]I3.I2.

Crystals of iodine-doped zirconium(IV) diphthalocyanine, [ZrPc(2)]I(3).I(2) (where Pc = C(32)H(16)N(8)), were grown directly in the reaction of pure zirconium powder with phthalonitrile under a stream of iodine at 260 degrees C. [ZrPc(2)]I(3).I(2) crystallizes in the space group P2(1)/m (No. 11) of the monoclinic system with lattice parameters of a = 6.735(1), b = 25.023(5), and c = 17.440(3) A, beta = 99.43(3) degrees, and Z = 2. The crystals of [ZrPc(2)]I(3).I(2) are built up from two pseudo-monodimensional aggregates: one-electron-oxidized [ZrPc(2)](+) units; weak interacting triiodide I(3)(-) ions with neutral diiodine molecules. The I(3)(-) ions and neutral I(2) molecules in the crystal of [ZrPc(2)]I(3).I(2) have been also detected by Raman spectroscopy. The [ZrPc(2)](+) units form stacks along the a axis, while the polymeric...I(3)(-)...I(2)...I(3)(-)...I(2)(-)... zigzag chains are located in the crystal along the b axis, so both pseudo-monodimensional aggregates are perpendicular to each other. This arrangement is different from that found in the tetragonal crystals of [ZrPc(2)](I(3))(2/3) in which both monodimensional aggregates, i.e., the stacks of partially oxidized [ZrPc(2)](2/3+) units and chains of symmetric triiodide ions, are parallel. EPR experiment together with the X-ray single-crystal analysis clearly shown that oxidation of the diamagnetic ZrPc(2) complex by iodine is ligand centered and homogeneously affecting both phthalocyaninato rings of ZrPc(2); thus, the formal oxidation state of both Pc rings in [ZrPc(2)]I(3).I(2) is nonintegral (-1.5). The UV-vis spectrum of [ZrPc(2)] I(3).I(2) is very similar to the spectrum of unoxidized ZrPc(2) complex in the B Soret and Q spectral region. However, in the spectrum of [ZrPc(2)] I(3).I(2) one additional band at approximately 502 nm is observed, which indicates the existence of the one-electron-oxidized phthalocyaninato(-) radical ligand and is assigned to the electronic transition from a deeper level to the half-occupied HOMO level. The single-crystal electrical conductivity data show anisotropy and nonmetallic character in conductivity (d sigma/dT > 0). The charge transport mainly proceeds along the pseudo-monodimensional stacks of [ZrPc(2)](+) units. The relatively high conductivity along the stacks of one-electron-oxidized [ZrPc(2)](+) units results from the staggering orientation of Pc rings (rotation angle 45.0(2) degrees ) that leads to the short inter-ring C(alpha)(pyrrole)[bond]C(alpha)(pyrrole) contacts (2.839(3)-3.024(3) A). These C(alpha)-pyrrole atoms make appreciable contribution to the partially occupied pi-molecular orbital of Pc macrocycle and the greatest overlap of the HOMO orbitals that form the conduction band of partially oxidized molecular crystals.

Journal Article↗
PubMed2002

Synthesis and structures of zirconium amide-iodide complexes.

Zirconium amide-iodide complexes were synthesized for possible use as chemical vapor deposition precursors to zirconium nitride films. The series of six complexes Zr(NR(2))(4-n)I(n)(R = Me or Et; n = 1-3) was prepared by reacting ZrI(4) and Zr(NR(2))(4) in hot toluene. X-ray crystallographic analyses were performed for Zr(NMe(2))(3)I, Zr(NEt(2))(2)I(2), and Zr(NEt(2))I(3). In the solid state, Zr(NMe(2))(3)I and Zr(NEt(2))(2)I(2) are the discrete dimers [Zr(NMe(2))(2)I(mu-NMe(2))](2) and [Zr(NEt(2))(2)I(mu-I)](2), and Zr(NEt(2))I(3) is the polymer of dimers ([Zr(NEt(2))I(2)(mu-I)](2))(n). In solution, Zr(NEt(2))(3)I is proposed to be monomeric on the basis of NMR data and a molecular weight determination. The complex Zr(NEt(2))(3)I is the most promising precursor candidate because of its physical properties.

Journal Article↗
PubMed2004

Cation mobility and kinetics of ion exchange in zirconium hydrogen monothiophosphate hydrate, Zr(HPO(3)S)(2)x1.5H(2)O.

The ion conductivity of zirconium hydrogen monothiophosphate (Zr(HPO(3)S)(2)x1.5H(2)O) has been measured by impedance spectroscopy. The measured value of proton conductivity is 3 x 10(-5) S/cm at 298 K. Conductivity was shown to decrease with increasing temperature due to a dehydration process. Above 450 K, the conductivity is likely governed by proton transport in the anhydrous phase Zr(HPO(3)S)(2). The activation energies of proton conductivity were measured to be 18 +/- 2 kJ/mol for Zr(HPO(3)S)(2)x1.5H(2)O and 60 +/- 3 kJ/mol for the anhydrous compound. The kinetics of ion exchange was studied with the use of potentiometric titration for several ion pairs, H(+)/Na(+), H(+)/Zn(2+), and Na(+)/Zn(2+) in Zr(HPO(3)S)(2)x1.5H(2)O. The diffusion coefficient values for H(+)/Na(+) ion exchange in Zr(HPO(3)S)(2)x1.5H(2)O are lower than those reported in alpha-zirconium phosphate. At the same time, the mobility of zinc ions in Zr(HPO(3)S)(2)x1.5H(2)O is higher than sodium ion mobility. The ion exchange H(+)/Zn(2+) is accompanied by the slow hydrolysis of the initial compound. In all cases, the powdered solids were evaluated by powder X-ray diffraction, and particle sizes were controlled by grinding and sieving the powders.

Journal Article↗
PubMed2005

"Oxidative addition" to a Zirconium(IV) redox-active ligand complex.

A strategy to enable reactivity analogous to oxidative addition is presented for d(0) transition-metal complexes. The reaction of the redox-active ligand 2,4-di-tert-butyl-6-tert-butylamidophenolate (ap) with ZrCl(4)(THF)(2) affords the new complex Zr(IV)(ap)(2)(THF)(2). This compound is formally zirconium(IV) and contains no d electrons; however, exposure of Zr(IV)(ap)(2)(THF)(2) to chlorine gas results in swift chlorine addition at the zirconium metal center via one-electron oxidation of each ap ligand. The diradical product, Zr(IV)Cl(2)(isq)(2) (isq = 2,4-di-tert-butyl-6-tert-butyliminosemiquinone), has been characterized by X-ray crystallography, electron paramagnetic resonance spectroscopy, and SQUID magnetometery.

Journal Article↗
PubMed2006

Chemistry of 2,2,6,6,-tetramethyl-3,5-heptanedione (Hthd) modification of zirconium and hafnium propoxide precursors.

The modification of different zirconium propoxide and hafnium propoxide precursors with 2,2,6,6,-tetramethyl-3,5-heptanedione (Hthd) was investigated by characterization of the isolated modified species. The complexes [Zr(OnPr)3(thd)](2), [Zr(OnPr)(OiPr)2(thd)]2, Zr(OiPr)(thd)3, [Hf(OnPr)3(thd)]2, and Hf(OiPr)(thd)3 were isolated and characterized. The structure of the n-propoxide analogue of Zr(OiPr)(thd)3 could not be refined, but its existence was clearly demonstrated by XRD and 1H NMR. The modification of the propoxide precursors involves mono- and trisubstituted intermediate compounds and does not involve a disubstituted compound; thus, the commercial product that is claimed to be "Zr(OiPr)2(thd)2" and is most commonly used for the MOCVD preparation of ZrO2 does not exist. No evidence was found for the presence of such a compound in either zirconium- or hafnium-based systems. Formation of the dimeric hydroxo-di-thd-substituted complex, [Hf(OH)(OiPr)(thd)2]2, which could be isolated only for hafnium-based systems, occurs on microhydrolysis. All heteroleptic intermediates are eventually transformed to the thermodynamically stable Zr(thd)4 or Hf(thd)4) The compounds obtained from isopropoxide precursors showed a higher stability than those with n-propoxide ligands or a combination of both types. In addition, it is important to note that residual alcohol facilitates the transformation and strongly enhances its rate. The unusually low solubility and volatility of MIV(thd)4 has been shown to be due to close packing and strong van der Waals interactions in the crystal structures of these compounds.

Journal Article↗
PubMed1999

Synthesis of Zirconium Aryloxide Complexes Containing Pendent Vinyl Groups.

The attachment of pendent olefin groups to oxygen-ligated zirconium complexes using olefin-substituted phenols and alcohols and readily accessible zirconium reagents is described. Syntheses of three crystallographically characterizable complexes isolable in 55-90% yield are reported. Eugenol, HOC(6)H(3)(OMe-2)(CH(2)CH=CH(2)-4) (HOAr) reacts with [Zr(O(i)Pr)(4)(HO(i)Pr)](2) in toluene to form [((i)PrO)(2)(ArO)Zr(&mgr;-O(i)Pr)](2), 1. CH(2)=CHCH(2)OH reacts with [Zr(NMe(2))(4)](2) in the presence of 2,6-dimethylphenol to form the mixed ligand salt, {Me(2)NH(2)}{[(2,6-Me(2)C(6)H(3)O)(3)Zr](2)(&mgr;-OCH(2)CH=CH(2))(3)}, 2. The potassium salt derived from eugenol, KOAr, reacts with "Zr(OEt)(4)" in THF to form [K(2)Zr(OAr)(4)(OEt)](2)(O), 3.

Journal Article↗