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A self-formation phenomenon leading to the hierarchically thermally stable macroporous zirconium phosphates with amorphous supermicroporous walls from the precursors of zirconium propoxide and orthophosphoric acid solution was observed.
The chiral phosphanylamido ligand, (N(CHMePh)(PPh2))-, has been introduced into co-ordination chemistry. As starting material the oily amines HN(R-*CHMePh)(PPh2)(1a) and HN(S-*CHMePh)(PPh2)(1b) were used. To reconfirm their absolute structure, 1b was oxidized with H2O2 in air to obtain HN(S-*CHMePh)(P(O)Ph2)(2) as a solid compound. The solid-state structure of 2 was established by single-crystal X-ray diffraction. The lithium salts of both enantiomers Li(N(R-*CHMePh)(PPh2))(3a) and Li(N(S-*CHMePh)(PPh2))(3b) were prepared by deprotonation reaction of 1a,b. Compounds 3a,b were further reacted with zirconocen dichloride to give the chiral metallocenes [(eta5-C5H5)2Zr(Cl)(eta2-N(R-*CHMePh)(PPh2))](4a) and [(eta5-C5H5)2Zr(Cl)(eta2-N(S-*CHMePh)(PPh2))](4b). In an alternative approach to give chiral zirconium compounds, the neutral amine 1b was reacted with [(PhCH2)4Zr] to give the enantiomeric pure complex [(PhCH2)3Zr(eta2-N(S-*CHMePh)(PPh2))](5). The solid-state structures of all zirconium complexes were determined by single-crystal X-ray diffraction.
Zirconium oxide clusters are generated in the gas phase by laser ablation of the metal into a flow of ca. 5% O2/95% He at 100 psig and supersonic expansion into a vacuum chamber. Mass spectra of neutral gas phase zirconium oxide clusters are obtained through photoionization at three different laser wavelengths: 118, 193, and 355 nm. Ionization of the clusters with 118 nm laser radiation is through a single photon ionization mechanism, while ionization by 193 and 355 nm laser radiation is through a multiphoton (three or more photon) mechanism. Fragment ion features are observed in the mass spectra of ZrmOn+ for only the 193 nm and 355 nm ionization schemes. The true neutral ZrmOn cluster distribution is obtained only through 118 nm single photon ionization, as verified by mass spectral peak linewidths and calculations of the cluster binding energies, ionization energies, and fragmentation rates. The neutral cluster distribution consists mainly of the series ZrmO2m and ZrmO(2m+1) for m = 1,..., approximately 30.
A new mixed barium zirconium oxalate, triaquatetra-mu-oxalato-dibarium(II)zirconium(IV), Ba(2)Zr(C(2)O(4))(4).3H(2)O or [Ba(2)Zr(C(2)O(4))(4)(H(2)O)(3)](n), has been synthesized. The complex is built from eightfold-coordinated Zr atoms and eleven- and sixfold-coordinated Ba atoms, linked by oxalate groups. The Zr atom, the two Ba atoms and one water O atom lie on crystallographic twofold axes, so that each coordination polyhedron has imposed C2 symmetry. Packing in the crystal is also assumed through hydrogen bonds.
Controlling gelation kinetics is an important objective for several applications (ceramic and thin film syntheses, reduction in permeability of porous rock, etc). There is a growing interest in studying the gelation of polymers by zirconium, a crosslinker of lower toxicity than the chromium which is still commonly used. XAS at the Zr K-edge was performed at the European Synchrotron Radiation Facility (ESRF) on the BM32 beamline. The fluorescence detection was used to carry out successful in situ speciation at concentrations as low as 36 ppm. The Zr speciation was determined both in ZrLa (where La stands for lactate) aqueous solutions and in gels of a terpolymer of acrylamide having 2% of zirconium reactive acrylate side groups and 2% of sulfonate groups introduced to prevent syneresis. XANES results show that Zr is always in a dodecahedral geometry. In ZrLa solutions. EXAFS results indicate that Zr species grow from a dimer Zr2(La)6 to a tetramer (Zr4(La)x) and then to larger polymers resulting from tetramer associations, as the Zr concentration decreases from 51840 ppm to 36ppm. In polymer gels, Zr species appear to be dimers at pH 6 while tetramers are found when gelation occurred at pH 7. Calculations taking into account multiple scattering effects as well as dynamic molecular calculation confirmed conclusions derived from conventional EXAFS analysis.
This report reviews the safety of Aluminum, Calcium, Lithium Magnesium, Lithium Magnesium Sodium, Magnesium Aluminum, Magnesium, Sodium Magnesium, and Zirconium Silicates, Magnesium Trisilicate, Attapulgite, Bentonite, Fuller's Earth, Hectorite, Kaolin, Montmorillonite, Pyrophyllite, and Zeolite as used in cosmetic formulations. The common aspect of all these claylike ingredients is that they contain silicon, oxygen, and one or more metals. Many silicates occur naturally and are mined; yet others are produced synthetically. Typical cosmetic uses of silicates include abrasive, opacifying agent, viscosity-increasing agent, anticaking agent, emulsion stabilizer, binder, and suspending agent. Clay silicates (silicates containing water in their structure) primarily function as adsorbents, opacifiers, and viscosity-increasing agents. Pyrophyllite is also used as a colorant. The International Agency for Research on Cancer has ruled Attapulgite fibers >5 microm as possibly carcinogenic to humans, but fibers <5 microm were not classified as to their carcinogenicity to humans. Likewise, Clinoptilolite, Phillipsite, Mordenite, Nonfibrous Japanese Zeolite, and synthetic Zeolites were not classified as to their carcinogenicity to humans. These ingredients are not significantly toxic in oral acute or short-term oral or parenteral toxicity studies in animals. Inhalation toxicity, however, is readily demonstrated in animals. Particle size, fibrogenicity, concentration, and mineral composition had the greatest effect on toxicity. Larger particle size and longer and wider fibers cause more adverse effects. Magnesium Aluminum Silicate was a weak primary skin irritant in rabbits and had no cumulative skin irritation in guinea pigs. No gross effects were reported in any of these studies. Sodium Magnesium Silicate had no primary skin irritation in rabbits and had no cumulative skin irritation in guinea pigs. Hectorite was nonirritating to the skin of rabbits in a Draize primary skin irritation study. Magnesium Aluminum Silicate and Sodium Magnesium Silicate caused minimal eye irritation in a Draize eye irritation test. Bentonite caused severe iritis after injection into the anterior chamber of the eyes of rabbits and when injected intralamellarly, widespread corneal infiltrates and retrocorneal membranes were recorded. In a primary eye irritation study in rabbits, Hectorite was moderately irritating without washing and practically nonirritating to the eye with a washout. Rats tolerated a single dose of Zeolite A without any adverse reaction in the eye. Calcium Silicate had no discernible effect on nidation or on maternal or fetal survival in rabbits. Magnesium Aluminum Silicate had neither a teratogenic nor adverse effects on the mouse fetus. Female rats receiving a 20% Kaolin diet exhibited maternal anemia but no significant reduction in birth weight of the pups was recorded. Type A Zeolite produced no adverse effects on the dam, embryo, or fetus in either rats or rabbits at any dose level. Clinoptilolite had no effect on female rat reproductive performance. These ingredients were not genotoxic in the Ames bacterial test system. In primary hepatocyte cultures, the addition of Attapulgite had no significant unscheduled DNA synthesis. Attapulgite did cause significant increases in unscheduled DNA synthesis in rat pleural mesothelial cells, but no significant increase in sister chromosome exchanges were seen. Zeolite particles (<10 microm) produced statistically significant increase in the percentage of aberrant metaphases in human peripheral blood lymphocytes and cells collected by peritoneal lavage from exposed mice. Topical application of Magnesium Aluminum Silicate to human skin daily for 1 week produced no adverse effects. Occupational exposure to mineral dusts has been studied extensively. Fibrosis and pneumoconiosis have been documented in workers involved in the mining and processing of Aluminum Silicate, Calcium Silicate, Zirconium Silicate, Fuller's Earth, Kaolin, Montmorillonite, Pyrophyllite, and Zeolite. The Cosmetic Ingredient Review (CIR. The Cosmetic Ingredient Review (CIR) Expert Panel concluded that the extensive pulmonary damage in humans was the result of direct occupational inhalation of the dusts and noted that lesions seen in animals were affected by particle size, fiber length, and concentration. The Panel considers that most of the formulations are not respirable and of the preparations that are respirable, the concentration of the ingredient is very low. Even so, the Panel considered that any spray containing these solids should be formulated to minimize their inhalation. With this admonition to the cosmetics industry, the CIR Expert Panel concluded that these ingredients are safe as currently used in cosmetic formulations. The Panel did note that the cosmetic ingredient, Talc, is a hydrated magnesium silicate. Because it has a unique crystalline structure that differs from ingredients addressed in this safety assessment, Talc is not included in this report.
Implants made form zirconium dioxide exhibit higher specific radionuclide activities of the uranium-radium and thorium series than metallic and aluminum implants. This study presents data on activity measurements performed on different samples of ZrO2 raw material (powder) and on the ceramic joint heads belonging to it to formulate a correlation between the specific radionuclide activities of the uranium-radium and thorium series in the raw material, the flux density of the alpha particle leaving the implant surface, and the annual dose of the tissue surrounding the implant. Based on this experimental study, an equation for defining the limits of the specific activities in raw material is proposed, taking into account the long-lived radionuclides (key nuclides) of the uranium-radium and thorium series weighted with their relative dose contributions from alpha emitters.
The new axially substituted phthalocyanine (pc) complex of zirconium(IV) with citric acid is reported. It has been shown that the replacement of two Cl-atoms with two citric acid fragments takes place as the result of the reaction between [ZrCl2(pc)] and citric acid. The complex [Zr(citrate)2(pc)] was formed. The spectroscopic properties of the synthesized compound in DMSO, RPMI 1640 medium with and without fetal calf serum (FCS), H2O, and buffer (Tris) solutions have been described. Antitumor activity of this compound has been studied. The cytostatic activity was observed in the concentration range of 6.1-9.0x10(9) molecules [Zr(citrate)2(pc)]/cell and occurred in 4-6 h after treatment with [Zr(citrate)2(pc)] solution.
A reliable two-stage carbon replica technique has been developed to extract precipitates from zirconium alloys. Using this technique, all precipitating phases can be extracted from Zircaloy-2, Zr-Cr-Fe, and Zr-Nb-Fe alloys. Precipitate identification using EDS X-ray analysis and convergent beam electron diffraction was greatly facilitated in comparison to thin foils. In addition, the sensitivity for the detection of trace elements in particles was increased using extraction replicas. The chemical compositions of the precipitates as determined from both replica and thin foils were in excellent agreement.
The damaging effects of some industrially important Aluminium and Zirconium compounds on guinea-pig macrophages and skin fibroblasts have been investigated. Cell death was measured by the release of lactate dehydrogenase activity. The haemolytic properties of these compounds has also been investigated. There is a correlation between the ability of these compounds to form granulomas after intradermal injection in the guinea-pig, their toxic effects on macrophages and fibroblasts and their haemolytic properties. A possible mechanism of toxicity of these compounds towards macrophages and fibroblasts is suggested.
Three samples of silica of different pore structure-predominantly microporous, S1; mesoporous, S2; and nonporous, S3-were modified with zirconium phosphate and examined. Pore structure analysis showed that modification had taken place in wider pores of S1 leaving a totally microporous sample, and in large pores of S2 giving a mesoporous sample of narrower pore size distribution. The modification of the nonporous sample decreased the surface area and pore volume to a lower extent than in the other two samples, but resulted in a surface of lower energy toward N2. The different distribution of surface silanol groups on the surfaces of different porosity may result in variable pictures on the modified surfaces as reflected in the differences observed in Brønsted acidity of modified surfaces. The use of these modified silica samples for amino acid adsorption (L-glutamic acid and L-alanine) indicated that both the isoelectric point of the amino acid and the distribution of surface groups on modified solids are controlling the adsorption process.
Bis-beta-diketonato complexes of titanium, zirconium, and hafnium were tested against autochthonous colorectal tumors in rats. The model was found to reflect the clinical situation most closely. Of the compounds tested, budotitane was the most effective in terms of decrease in tumor weight and number and in increasing the lifespan of the treated animals. The therapeutic efficiency was superior to that of 5-fluorouracil, which so far has been the drug with the best activity in patients suffering from colon cancer.
The action of Zirconium (Zr) on biological systems presents an enigma. It is ubiquitous, being present in nature in amounts higher than most trace elements. It is taken up by plants from soil and water and accumulated in certain tissues. The entry into animal systems in vivo is related to the mode of exposure and the concentration in the surrounding environment. Retention is initially in soft tissues and then slowly in the bone. The metal is able to cross the blood brain-barrier and is deposited in the brain and the placental barrier to enter milk. The daily human uptake has been known to be as high as 125 mg. The level of toxicity has been found to be moderately low, both in histological and cytological studies. The toxic effects induced by very high concentrations are nonspecific in nature. Despite the presence and retention in relatively high quantities in biological systems, Zr has not yet been associated with any specific metabolic function. Very little information is available about its interaction with the compounds of the genetical systems, such as nucleic acids. Apparently, the metal is neither an essential nor toxic element in the conventional sense. However, the increasing exposure to this element through its increasing use in new materials and following radioactive fallout, has increased the importance of the study of its effects on living organisms. The tetravalent nature of the ionic state and the high stability of the compounds formed are important factors that need to be considered, as also the accumulation of this element in the brain, reminiscent of the relationship between Al3+ and Alzheimer's disease.
A direct solid sampling electrothermal atomic absorption spectrometric method for determination of Cd, Co, Cr, Cu, Fe, Li, Mn, Ni and Zn in zirconium dioxide has been developed. Using optimised experimental conditions, very effective in-situ analyte/matrix separation was achieved without any chemical modification. After the measurement, the matrix residue could easily be tipped out from the platform. In the determination of Cr, before sampling, the platform bottom was covered with carbon powder. Quantification was performed using calibration curves measured with aqueous standard solutions pipetted onto the matrix residue from a previous sample run. Sample amounts between 0.5 and 40 mg were applied for each analysis cycle. The accuracy was determined by comparison of the results with those obtained by radiochemical neutron activation analysis and by electrothermal atomic absorption spectrometry using liquid sampling of digests and slurry sampling. For the nine elements assayed, the limits of detection achievable by this method are between 0.06 ng g(-1) (Cd) and 2.3 ng g(-1) (Fe).
Bulk screen-printed electrodes (bSPEs) modified with zirconium phosphate (ZrP) and Meldola blue (MB) and by electrochemical deposition of a Reineckate film (bMBZrPRs-SPEs) have been constructed and used as NADH sensors. Cyclic voltammetric investigation of these bulk electrochemically modified screen-printed electrodes revealed stable catalytic activity in oxidation of the reduced form of the coenzyme nicotinamide adenine dinucleotide (NADH). Flow-injection analysis (FIA) coupled with amperometric detection confirmed the improved stability of the bMBZrPRs-SPEs (10(-4) mol L(-1) NADH, %RSD = 4.2, n = 90, pH 7.0). Other conditions, for example applied working potential (+50 mV relative to Ag|AgCl), flow rate (0.30 mL min(-1)) and pH-dependence (range 4.0-10.0) were evaluated and optimized. A glycerol biosensor, prepared by immobilizing glycerol dehydrogenase (GDH) on the working electrode area of a bMBZrPRs-SPE, was also assembled. The biosensor was most stable at pH 8.5 (%RSD = 5.6, n = 70, 0.25 mmol L(-1) glycerol). The detection and quantification limits were 2.8 x 10(-6) and 9.4 x 10(-6) mol L(-1), respectively, and the linear working range was between 1.0 x 10(-5) and 1.0 x 10(-4) mol L(-1). To assess the effect of interferences, and recovery by the probe we analyzed samples taken during fermentation of chemically defined grape juice medium and compared the results with those obtained by HPLC.
In this work, n-alkylamines (number of carbon atoms ranging from 3 to 10) were investigated in detail by molecular modeling as spacers for intercalating porphyrins into alpha-zirconium phosphate (alpha-ZrP). Pre-intercalated n-alkylamines can form either a flat monolayer or a canted bilayer in the gallery of alpha-ZrP. Based on the interlayer state and intercalative potential of the two modes in alpha-ZrP, it is suggested that the flat monolayer is a better spacer than the bilayer and that n-propylamine (PA) and n-butylamine (BA) in mobile monolayers are the best spacers among the n-alkylamines studied, as is also found experimentally. The intercalation behavior of TMPyP [5,10,15,20-tetrakis (1-methylpyridinium-4-yl) porphyrin] and several other porphyrins was investigated by calculating the intercalative potential. The calculated results showed that the porphyrins were densely packed in a canted monolayer model, and an increase of polarity of the substituent would facilitate the intercalation of the porphyrins.
A spectrofluorimetric method has been developed for the determination of 3-hydroxy-2-naphthoic acid (3H2NA) by formation of a ternary complex with zirconium (IV) and beta-cyclodextrin (beta-CD). It has been observed that the fluorescence intensity of 3H2NA is greatly enhanced when the ternary complex is formed and is accompanied with shifts in the excitation and emission wavelengths. The conditions for the formation of the ternary complex have been optimized and the stoichiometry has been calculated, resulting a 1:2:1 complex (3H2NA:Zr: beta-CD). The linear range was 20-2000 ng mL(-1) and the detection and quantification limits calculated were 17 and 58 ng mL(-1), respectively. The proposed method was applied to the determination of 3H2NA in river water. To eliminate interferences an off-line solid phase extraction (SPE) procedure using C18 cartridges was used. The extraction procedure was optimized and good recoveries were obtained (around 100%) with relative standard deviations (RSDs) of less than 5%.
The applicability of an eluotropic scale pertaining to the desorption of low molecular weight Lewis base solutes from zirconium oxide is examined for its ability to rationalize the retention of proteins on this substrate. The strongest Lewis base eluents (phosphate and fluoride) are able to bring about elution of nearly all proteins provided that their initial mobile phase concentration almost saturates the eluent's adsorption isotherm. In contrast, weaker Lewis bases such as borate, sulfate and bromide are able to elute only those proteins which are retained primarily by ionic interactions. In weak eluents, proteins that contain a large number of accessible Lewis base sites are not eluted from the support. The effect of ionic strength and a variety of Lewis base eluents were also examined.